U.S. patent application number 10/847195 was filed with the patent office on 2004-11-04 for low-hygroscopicity low-birefringence resin compositions, molding material, sheet or film obtained therefrom, and optical part.
Invention is credited to Iwata, Shuichi, Ushikubo, Keiko, Yamanaka, Tetsuo, Yamashita, Yukihiko, Yoshida, Akihiro.
Application Number | 20040220342 10/847195 |
Document ID | / |
Family ID | 27528797 |
Filed Date | 2004-11-04 |
United States Patent
Application |
20040220342 |
Kind Code |
A1 |
Yamashita, Yukihiko ; et
al. |
November 4, 2004 |
Low-hygroscopicity low-birefringence resin compositions, molding
material, sheet or film obtained therefrom, and optical part
Abstract
Low-hygroscopicity low-birefringence resin compositions. One of
the compositions is a resin composition (a) comprising the
following polymers (A), and (B) and/or (C). Another is a resin
composition (b) comprising the following polymers (A), (B) and (H).
Still another is a polymer comprising the following polymers (I)
and (J), diphenylsilicone (D), and a phenolic antioxidant (E). (A)
A polymer comprising one or more kinds of indene and indene
derivatives represented by the following general formula (I). (B) A
polymer comprising polystyrene or a polystyrene derivative. (C) A
polymer comprising a monomer copolymerizable with styrene or a
styrene derivative. (H) A graft polymer having a structure wherein
a polymer comprising at least one kind of indene and an indene
derivative represented by the general formula (I) bonds to a side
chain of a polymer comprising a monomer copolymerizable with
styrene or a styrene derivative. (I) A polymer comprising one or
more kinds of indene and indene derivatives represented by the
general formula (I), wherein the polymer has a heterocyclic
structure in a side chain thereof. (J) A polymer comprising styrene
or a styrene derivative, and a monomer copolymerizable with styrene
or a styrene derivative, wherein the polymer has a carboxyl group
and/or a phenolic hydroxyl group in a side chain
Inventors: |
Yamashita, Yukihiko;
(Ichihara-shi, JP) ; Iwata, Shuichi;
(Ichihara-shi, JP) ; Yamanaka, Tetsuo;
(Ichihara-shi, JP) ; Yoshida, Akihiro;
(Ichihara-shi, JP) ; Ushikubo, Keiko; (Mobara-shi,
JP) |
Correspondence
Address: |
KNOBBE MARTENS OLSON & BEAR LLP
2040 MAIN STREET
FOURTEENTH FLOOR
IRVINE
CA
92614
US
|
Family ID: |
27528797 |
Appl. No.: |
10/847195 |
Filed: |
May 17, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10847195 |
May 17, 2004 |
|
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10019753 |
Mar 5, 2002 |
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10019753 |
Mar 5, 2002 |
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PCT/JP00/04215 |
Jun 27, 2000 |
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Current U.S.
Class: |
525/210 ;
G9B/7.172 |
Current CPC
Class: |
C08L 25/04 20130101;
C08L 45/00 20130101; C08L 25/00 20130101; G02B 1/04 20130101; C08L
45/00 20130101; C08L 2666/04 20130101 |
Class at
Publication: |
525/210 |
International
Class: |
C08L 045/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 28, 1999 |
JP |
11-181181 |
Jun 28, 1999 |
JP |
11-181182 |
Jan 28, 2000 |
JP |
2000-24774 |
Jan 28, 2000 |
JP |
2000-24775 |
Jan 28, 2000 |
JP |
2000-24776 |
Claims
1. A resin composition (a) for use in optical parts, comprising the
following polymers (A) and either or both of (B) and (C): (A) a
polymer comprising monomer units which are one or more kinds of
indene and indene derivatives represented by the following general
formula (I); (B) a polymer consisting of monomer units which are
styrene or styrene derivatives; (C) a polymer comprising monomer
units which are styrene or styrene derivatives, and a monomer unit
copolymerizable with styrene or a styrene derivative selected from
the group consisting of styrene, nucleus-substituted alkylstyrenes,
nucleus-substituted aromatic styrenes, .alpha.-substituted
alkylstyrenes, .beta.-substituted alkylstyrenes,
nucleus-substituted alkoxystyrenes, alkyl vinyl ethers, aromatic
vinyl ethers, isobutene, diisobutylene, and (meth)acrylic esters
having 1 to 8 carbon atoms: 2wherein R.sub.1, R.sub.2, R.sub.3,
R.sub.4, and R.sub.5 may be the same or different, and each
represents a hydrogen atom; a monovalent hydrocarbon group
containing a nitrogen atom, an oxygen atom or a silicon atom; an
alkyl group having 1 to 6 carbon atoms; or a monovalent aromatic
hydrocarbon group; X represents a hydrogen atom, a halogen atom, an
acyl group, an alkoxy group or a nitrile group; x represents an
integer of 0 to 4, and y represents an integer of 1 to 4, where
x+y=4, wherein the saturated water absorption is 0.4% or less, and
the birefringence in stretching the resin composition by 200% is in
the range of -2.times.10.sup.-6 to 2.times.10.sup.-6.
2. The resin composition (a) according to claim 1, wherein a
diphenylsilicone (D) and/or a phenolic antioxidant (E) are/is added
to the resin composition comprising the polymers (A) and either or
both (B) and (C).
3. (Cancelled)
4. The resin composition (a) according to claim 1, wherein the
weight-average molecular weight of the polymer (A) is lower than
80000.
5. The resin composition (a) according to claim 1, wherein the
weight-average molecular weight(s) of the polymer (B) and/or the
polymer (C) are/is 50000 or higher.
6. The resin composition (a) according to claim 1, wherein the
content of the polymer (A) is 30 to 90% by weight of the total of
the resin composition (a).
7-18. (Canceled).
19. A molding material for use in optical parts, the molding
material being obtained by molding a resin composition (a)
according to claim 1.
20. A sheet for use in optical parts, the sheet being obtained from
a resin composition (a) according to claim 1.
21. A film for use in optical parts, the film being obtained from a
resin composition (a) according to claim 1.
22. (Canceled)
Description
TECHNICAL FIELD
[0001] The present invention relates to resin compositions having
low hygroscopicity, low birefringence and low permittivity, being
excellent in fluidity, causing little change in color in heating,
and being excellent in mold release characteristics in injection
molding, and to a molding material, a sheet, or a film obtained by
molding these resin compositions and to an optical part.
BACKGROUND ART
[0002] Many of the monomers having an unsaturated bond with
reaction activity can yield a polymer by selecting a catalyst that
can cause cleavage of the unsaturated bond to initiate a chain
reaction and appropriate reaction conditions. In general, there are
an extremely wide variety of kinds of the monomers having an
unsaturated bond, so that kinds of the resins that can be obtained
therefrom also come in a great many varieties. However,there are
relatively few kinds of monomers that can yield a product having a
high molecular weight of 10,000 or higher, which is generally
called as a high molecular compound. For example, typical monomers
include ethylene, substituted ethylenes, propylene, substituted
propylenes, styrene, alkylstyrenes, alkoxystyrenes, norbornene,
various acrylic esters, butadiene, cyclopentadiene,
dicyclopentadiene, isoprene, maleic anhydride, maleimide, fumarate
esters, allyl compounds, and the like. Various kinds of resins are
synthesized from these monomers or various combinations
thereof.
[0003] The use of these resins is mainly limited to the field of
relatively inexpensive commercial equipment, and there is little
application to the field of high technology such as
semiconductor-related materials and the like. This is because heat
resistance, low hygroscopicity and permittivity have not been
simultaneously achieved.
[0004] For instance, in the field of semiconductor-related
materials, on account of increased density in integration in recent
years, it has been desired to further attain low permittivity in
addition to heat resistance and low hygroscopicity that have
already been achieved. In order to achieve low permittivity, it is
indispensable in principle to decrease the number of polar groups
in a resin. At present, polyimides are often employed as resins for
semiconductors. However, a lot of hard work has been made to
achieve low permittivity because polyimides contain many carbonyl
groups in a resin skeleton. As measures to overcome the situation,
researches using the monomers containing fluorine have been done
extensively, but sufficiently low permittivity has not been
achieved. Moreover, there are some problems such as the rising
price of resins, complicated synthesis of resins, and the like.
[0005] As another method, attempts to synthesize a polymer
comprising a hydrocarbon containing no polar groups have been made.
An example of such a polymer is a series of polymers called cyclic
polyolefins. Specific examples include a polymer obtained by
hydrogenating polynorbornene, or a polymer comprising
polydicyclopentene and a derivative thereof. Although these
polymers can exhibit extremely low permittivity, they have problems
such as low heat resistance and very high permeability of water in
spite of extremely low water absorption. In particular, the high
permeability of water is a common characteristic of polyolefins,
and it is considered to be extremely difficult to solve this
problem.
[0006] Another example is a syndiotactic polystyrene synthesized by
using Ziegler-Natta catalyst or Kaminsky catalysts. This polymer
has a structure that three-dimensional positions of the benzene
rings to the backbone are located alternately in the opposite
directions, so that it is possible to attain very high heat
resistance and at the same time extremely low water absorption,
extremely low permeability of water and very low level of
permittivity. However, this polymer has such high crystallinity
that it has a problem of considerably poor adhesion to a base
material and also has another problem that methods of processing it
are markedly limited because it is insoluble in any solvents. That
is, at present, a polymer that can overcome the above-mentioned
problems has not been developed yet.
[0007] On the other hand, typical polymers for optical uses, such
as optical lenses, optical waveguide materials and the like include
acrylic resins and polyolefin resins. Acrylic resins have
characteristics of having excellent transparency and workability
and extremely low birefringence. However, they have disadvantages
that they have high hygroscopicity, relatively low heat resistance
and low toughness. By contrast, polyolefin resins have excellent
heat resistance and extremely low hygroscopicity, but they are
inferior to acrylic resins in transparency and low birefringence.
That is, both of acrylic resins and polyolefin resins have both
advantages and disadvantages, and thus it has strongly been desired
to develop a resin compensating for the disadvantages of acrylic
resins and polyolefin resins.
[0008] Thus, in order to improve acrylic resins, that is, to
overcome the disadvantages such as high hygroscopicity and low heat
resistance, a lot of investigations have been carried out. For
example, there is a method of improving hygroscopicity and heat
resistance by using a monomer having a bulky substituent (disclosed
in Japanese Patent No. 2678029). Although this invention is indeed
effective to a certain extent, the improved acrylic resin is still
interior to polyolefin resins in hygroscopicity. This invention
poses still another problem that there is a drastic reduction in
toughness and strength because a bulky substituent is present in a
side chain, so that the resin becomes likely to be broken
particularly in molding processing. Although there is a method of
attempting to give toughness to the resin by copolymerizing a
monomer that gives flexibility for the purpose of improving this,
decrease in heat resistance is inevitable, and thus the effect of
introducing a bulky substituent is weakened.
[0009] Polyolefin resins have extremely great advantages of low
hygroscopicity and high heat resistance as resins of optical use,
but the high birefringence thereof has become a great disadvantage
with the increasing sophistication of optical devices in recent
years. Therefore, many attempts to lower the birefringence of
polyolefin resins have been made particularly recently.
[0010] Such an example is disclosed in Japanese Patent Application
Laid-open No. Hei 8-110402. This invention is that a resin or a low
molecular weight compound having birefringence with the opposite
sign to the birefringence of a polyolefin resins mixed to the
polyolefin resin to compensate the birefringence intrinsic to the
resin, thereby reducing the birefringence of the resin mixture to
zero. In this method, it is required that a resin to be mixed and a
polyolefin resin be completely compatible. However, compatibility
of a polyolefin resin and a resin that is claimed is insufficient
in the above invention, so that satisfactory effect cannot be
achieved.
[0011] Thus, in order to realize as complete compatibility as
possible, a method of adding a compatibility agent as the third
component is carried out as a polymer alloying technique, and it is
specifically described in U.S. Pat. No. 4,373,065. In order to mix
both of the above highly homogeneously, both should be in a molten
state or a solution state. However, it is considered that it is
extremely difficult to obtain a practical polymer material that is
highly homogeneous and has no birefringence as a whole by using any
physical method.
[0012] A method to solve these problems is disclosed in, Japanese
Patent Application No. Hei 8-199901. This method has some problems
such as remaining a portion of a resin in a die when removing a
product from the die in injection molding of the resin composition
or breaking a product in mold releasing. Moreover, it has a
disadvantage in that the color of a product changes while the resin
stays in a molding machine for a long time.
DISCLOSURE OF THE INVENTION
[0013] The present invention provider resin compositions having low
hygroscopicity, low birefringence and low permittivity, excelling
in fluidity, causing little change in color upon heating, and being
excellent in mold release characteristics in injection molding, a
molding material, a sheet or a film obtained by molding these resin
compositions, and an optical part.
[0014] The present invention relates to the following items (1) to
(22).
[0015] (1) A resin composition (a) comprising the following
polymers (A), and (B) and/or (C):
[0016] (A) a polymer comprising one or more kinds of indene and
indene derivatives represented by the following general formula
(I);
[0017] (B) a polymer comprising polystyrene or a polystyrene
derivative; and
[0018] (C) a polymer comprising a monomer copolymerizable with
styrene or a styrene derivative: 1
[0019] (wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and
R.sub.6 may be the same or different, and each represents a
hydrogen atom; a monovalent hydrocarbon group containing a nitrogen
atom, an oxygen atom or a silicon atom; an alkyl group having 1 to
6 carbon atoms; or a monovalent aromatic hydrocarbon group. X
represents a hydrogen atom, a halogen atom, an acyl group, an
alkoxy group or a nitrile group. x represents 0 or an integer of 1
to 4, and y represents an integer of 1 to 4, where x+y=4.).
[0020] (2) The resin composition (a) according to (1), wherein a
diphenylsilicone (D) and/or a phenolic antioxidant (E) are/is added
to the resin composition comprising the polymers (A), and (B)
and/or (C).
[0021] (3) The resin composition (a) according to (1) or (2),
wherein the saturated water absorption is 0.4% or less, and the
birefringence in stretching the resin composition by 200% is in the
range of -2.times.10.sup.-6 to 2.times.10.sup.-5.
[0022] (4) The resin composition (a) according to any one of (1) to
(3), wherein the weight-average molecular weight of the polymer (A)
is lower than 80000.
[0023] (5) The resin composition (a) according to any one of (1) to
(4), wherein the weight-average molecular weight(s) of the polymer
(B) and/or the polymer (c) are/is 50000 or higher.
[0024] (6) The resin composition (a) according to any one of (1) to
(5), wherein the content of the polymer (A) is 30 to 90% by weight
of the total of the resin composition (a).
[0025] (7) A resin composition (b) comprising the following
polymers (F), (G) and (H):
[0026] (F) a polymer comprising one or more kinds of indene and
indene derivatives represented by the above general formula
(I);
[0027] (G) a polymer comprising polystyrene or a polystyrene
derivative; and
[0028] (H) a graft polymer having a structure where a polymer
comprising at least one kind of indene and indene derivatives
represented by the general formula (I) bonds to a side chain of a
polymer comprising a monomer copolymerizable with styrene or a
styrene derivative.
[0029] (8) The resin composition (b) according to (7), wherein a
diphenylsilicone (D) and/or a phenolic antioxidant (E) are/is added
to the resin composition comprising the polymers (F), (G) and
(H).
[0030] (9) The resin composition (b) according to (7) or (8),
wherein the saturated water absorption is 0.4% or less, and the
birefringence in stretching the resin composition by 200% is in the
range of -2.times.10.sup.-6 to 2.times.10.sup.-6.
[0031] (10) The resin composition (b) according to any one of (7)
to (9), wherein the weight-average molecular weight of the polymer
(F) is 4000 or higher.
[0032] (11) The resin composition (b) according to any one of (7)
to (10), wherein the weight-average molecular weights of the
polymer (G) and the polymer (H) are 50000 or higher.
[0033] (12) The resin composition (b) according to any one of (7)
to (11), wherein the content of the polymer (F) is 30 to 90% by
weight of the total of the resin composition (b).
[0034] (13) A resin composition (c) comprising the following
polymers (I) and (J), diphenylsilicone (D), and a phenolic
antioxidant (E):
[0035] (I) a polymer comprising one or more kinds of indene and
indene derivatives represented by the above general formula (I),
wherein the polymer has a heterocyclic structure in a side chain
thereof; and
[0036] (J) a polymer comprising styrene or a styrene derivative,
and a monomer copolymerizable with styrene or a styrene derivative,
wherein the polymer has a carboxyl group and/or a phenolic hydroxyl
group in a side chain thereof.
[0037] (14) The resin composition (c) according to (13), wherein
the saturated water absorption is 0.4% or less, and the
birefringence in stretching the resin composition by 200% is in the
range of -2.times.10.sup.-6 to 2.times.10.sup.-6.
[0038] (15)The resin composition (c) according to (13) or (14),
wherein the content of the heterocyclic structure in the polymer
(I) is 0.01 to 5 mol % of the total of the resin composition (c),
and the content of the carboxyl group and/or the phenolic hydroxyl
group in the polymer (J) is 0.01 to 5 mol % of the total of the
resin composition (c).
[0039] (16) The resin composition (c) according to any one of (13)
to (15), wherein the molar ratio of the heterocyclic structure to
the carboxyl group and/or the phenolic hydroxyl group is 0.1 to
10.0.
[0040] (17) The resin composition (c) according to any one of (13)
to (16), wherein the content of the polymer (I) is 30 to 90% by
weight of the total of the resin composition (c).
[0041] (18) The resin composition (c) according to any one of (13)
to (17), wherein the addition amount of the diphenylsilicone (D) is
0.01 to 1.0% by weight of the total of the resin composition (c),
and the addition amount of the phenolic antioxidant (E) is 0.1 to
3.0% by weight of the total of the resin composition (c).
[0042] (19) A molding material obtained by molding a resin
composition selected from the resin composition (a) according to
(1), the resin composition (b) according to (7) and the resin
composition (c) according to (13).
[0043] (20). A sheet obtained from a resin composition selected
from the resin composition (a) according to (1), the resin
composition (b) according to (7) and the resin composition (c)
according to (13).
[0044] (21) A film obtained from a resin composition selected from
the resin composition (a) according to (1), the resin composition
(b) according to (7) and the resin composition (c) according to
(13).
[0045] (22) An optical part using the molding material, the sheet
or the film according to any one of (19) to (21).
[0046] Hereinbelow, the present invention will be described in
detail.
[0047] <1> The Resin Composition (a) of the Present
Invention
[0048] A resin composition (a) of the present invention is a resin
composition comprising the following polymers (A), and (B) and/or
(C):
[0049] (A) a polymer comprising one or more kinds of indene and
indene derivatives represented by the general formula (I) described
above;
[0050] (B) a polymer comprising polystyrene or a polystyrene
derivative; and
[0051] (C) a polymer comprising a monomer copolymerizable with
styrene or a styrene derivative.
[0052] In the resin composition (a) of the present invention, the
above polymer (A) is not particularly limited and any polymer may
be employed as the polymer (A), as long as it may be any polymer
containing one or more kinds of indene and indene derivatives
represented by the above general formula (I).
[0053] The indene derivatives for use in the above polymer (A)
include those represented by the above general formula (I), wherein
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 may be the
same or different, and each represents a hydrogen atom; a
monovalent hydrocarbon group containing a nitrogen atom, an oxygen
atom or a silicon atom; an alkyl group having 1 to 6 carbon atoms;
or a monovalent aromatic hydrocarbon group.
[0054] Monovalent hydrocarbon groups containing a nitrogen atom, an
oxygen atom or a silicon atom include, for example,
dimethylaminoethyl group, diethylaminoethyl group, methoxy group,
ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy
group, trimethylsilyl group, triethylsilyl group, and the like.
[0055] Alkyl groups having 1 to 6 carbon atoms include, for
example, methyl group, ethyl group, propyl group, n-butyl group,
isobutyl group, t-butyl group, n-pentyl group, 2-methylbutyl group,
3-methylbutyl group, t-pentyl group, n-hexyl group, 2-methylpentyl
group, 3-methylpentyl group, 4-methylpentyl group, 1-methylpentyl
group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group,
2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 3,4-dimethylbutyl
group, 4,4-dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl
group, cyclohexyl group, and the like.
[0056] Monovalent aromatic hydrocarbon groups include phenyl group,
naphthyl group, benzyl group, and the like. Those listed
hereinbefore are simply examples, and monovolent aromatic
hydrocarbon groups are not limited thereto.
[0057] X represents a hydrogen atom, a halogen atom, an acyl group,
an alkoxy group or a nitrile group. Halogen atoms in X include
fluorine, chlorine, bromine, and iodine.
[0058] Acyl groups in X include formyl group, acetyl group,
propionyl group, butyryl group, isobutyryl group, and the like.
[0059] Alkoxy groups in X include methoxy group, ethoxy group,
propoxy group, butoxy group, pentoxy group, hexoxy group, and the
like.
[0060] Furthermore, x represents 0 or an integer of 1 to 4, and y
represents an integer of 1 to 4, where x+y=4.
[0061] The above indene or indene derivatives may be used singly or
in combination with two or more as a monomer for use in the polymer
(A).
[0062] The above indene derivatives having a substituent include
nucleus-substituted alkylindenes such as nucleus-substituted
methylindene, nucleus-substituted ethylindehe, nucleus-substituted
propylindene, nucleus-substituted butylindene and the like,
nucleus-substituted chloroindene, nucleus-substituted bromoindene,
and the like. More specifically, they preferably include
methylindene, .alpha.-methylindene, .beta.-methylindene, and the
like.
[0063] The polymer (B) for use in the resin composition (a) is a
polymer comprising polystyrene or a polystyrene derivative. In the
present invention, monomers for use in the production of the
polymer (B) comprising polystyrene or a polystyrene derivative
include, for example, styrene, nucleus-substituted alkylstyrenes,
nucleus-substituted aromatic styrenes, .alpha.-substituted
alkylstyrenes, .beta.-substituted alkylstyrenes,
nucleus-substituted alkoxystyrenes, and the like.
[0064] Nucleus-substituted alkylstyrenes that may be employed
include, for example, o-methylstyrene, m-methylstyrene,
p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene,
o-propylstyrene, m-propylstyrene, p-propylstyrene,
o-n-butylstyrene, m-n-butylstyrene, p-n-butylstyrene,
o-isobutylstyrene, m-isobutylstyrene, p-isobutylstyrene,
o-t-butylstyrene, m-t-butylstyrene, p-t-butylstyrene,
o-n-pentylstyrene, m-n-pentylstyrene, p-n-pentylstyrene,
o-2-methylbutylstyrene, m-2-methylbutylstyrene,
p-2-methylbutylstyrene, o-3-methylbutylstyrene,
m-3-methylbutylstyrene, p-3-methylbutyletyrene, o-t-pentylstyrene,
m-t-pentylstyrene, p-t-pentylstyrene, o-n-hexylstyrene,
m-n-hexylstyrene, p-n-hexylstyrene, o-2-methylpentylstyrene,
m-2-methylpentylstyrene, p-2-methylpentylstyrene- ,
o-3-methylpentylstyrene, m-3-methylpentylstyrene,
p-3-methylpentylstyrene, o-1-methylpentylstyrene,
m-1-methylpentylstyrene- , p-1-methylpentylstyrene,
o-2,2-dimethylbutylstyrene, m-2,2-dimethylbutylstyrene,
p-2,2-dimethylbutylstyrene, o-2,3-dimethylbutylstyrene,
m-2,3-dimethylbutylstyrene, p-2,3-dimethylbutylstyrene,
o-2,4-dimethylbutylstyrene, m-2,4-dimethylbutylstyrene,
p-2,4-dimethylbutylstyrene, o-3,3-dimethylbutylstyrene,
m-3,3-dimethylbutylstyrene, p-3,3-dimethylbutylstyrene,
o-3,4-dimethylbutylstyrene, m-3,4-dimethylbutylstyrene,
p-3,4-dimethylbutylstyrene, o-4,4-dimethylbutylstyrene,
m-4,4-dimethylbutylstyrene, p-4,4-dimethylbutylstyrene,
o-2-ethylbutylstyrene, m-2-ethylbutylstyrene,
p-2-ethylbutylstyrene, o-1-ethylbutylstyrene,
m-1-ethylbutylstyrene, p-1-ethylbutylstyrene, o-cyclohexylstyrene,
m-cyclohexylstyrene, p-cyclohexylstyrene, and the like. Those
listed hereinbefore are simply examples, and nucleus-substituted
alkylstyrenes are not limited thereto. These may be used singly or
in combination with two or more.
[0065] Nucleus-substituted aromatic styrenes that may be employed
include, for example, o-phenylstyrene, m-phenylstyrene,
p-phenylstyrene, and the like. Those listed hereinbefore are simply
examples, and nucleus-substituted aromatic styrenes are not limited
thereto.
[0066] .alpha.-substituted alkylstyrenes that may be employed
include, for example, .alpha.-methylstyrene, .alpha.-ethylstyrene,
.alpha.-propylstyrene, .alpha.-n-butylstyrene,
.alpha.-isobutylstyrene, .alpha.-t-butylstyrene,
.alpha.-n-pentylstyrene, .alpha.-2-methylbutylsty- rene,
.alpha.-3-methylbutylstyrene, .alpha.-t-butylstyrene,
.alpha.-t-pentylstyrene, .alpha.-n-hexylstyrene,
.alpha.-2-methylpentylot- yrene, .alpha.-3-methylpentylstyrene,
.alpha.-1-methylpentylstyrene, .alpha.-2,2-dimethylbutylstyrene,
.alpha.-2,3-dimethylbutylstyrene, .alpha.-2,4-dimethylbutylstyrene,
.alpha.-3,3-dimethylbutylstyrene, .alpha.-3,4-dimethylbutylstyrene,
.alpha.-4,4-dimethylbutylstyrene, .alpha.-2-othylbutylstyrene,
.alpha.-1-ethylbutylstyrene, .alpha.-cyclohexylstyrene, and the
like. Those listed hereinbefore are simply examples, and
.alpha.-substituted alkylstyrenes are not limited thereto. These
may be used singly or in combination with two or more.
[0067] .beta.-substituted alkylstyrenes that may be employed
include, for example, .beta.-methylstyrene, .beta.-ethylstyrene,
.beta.-propylstyrene, .beta.-n-butylstyrene,
.beta.-isobutylstyrene, .beta.-t-butylstyrene,
.beta.-n-pentylstyrene, .beta.-2-methylbutylstyrene,
.beta.-3-methylbutylstyrene, .beta.-t-pentylstyrene,
.beta.-n-hexylstyrene, .beta.-2-methylpentylstyrene,
.beta.-3-methylpentylstyrene, .beta.-1-methylpentylstyrene,
.beta.-2,2-dimethylbutylstyreae, .beta.-2,3-dimethylbutylstyrene,
.beta.-2,4-dimethylbutylstyrene, .beta.-3,3-dimethylbutylstyrene,
.beta.-3,4-dimethylbutylstyrene, .beta.-4,4-dimethylbutylstyrene,
.beta.-2-ethylbutylstyrene, .beta.-1-ethylbutylstyrene,
.beta.-cyclohexylstyrene, and the like. Those listed hereinbefore
are simply examples, and .beta.-substituted alkylstyrenes are not
limited thereto. These may be used singly or in combination with
two or more.
[0068] Nucleus-substituted alkoxystyrenes that may be employed
include, for example, o-methoxystyrene, m-methoxystyrene,
p-methoxystyrene, o-ethoxystyrene, m-ethoxystyrene,
p-ethoxystyrene, o-propoxystyrene, m-propoxystyrene,
p-propoxystyrene, o-n-butoxystyrene, m-n-butoxystyrene,
p-n-butoxystyrene, o-isobutoxystyrene, m-isobutoxystyrene,
p-isobutoxystyrene, o-t-butoxystyrene, m-t-butoxystyrene,
p-t-butoxystyrene, o-n-pentoxystyrene, m-n-pentoxystyrene,
p-n-pentoxystyrene, o-2-methylbutoxystyrene,
m-2-methylbutoxystyrene, p-2-methylbutoxystyrene,
o-3-methylbutoxystyrene, m-3-methylbutoxystyrene- ,
p-3-methylbutoxystyrene, o-t-pentoxystyrene, m-t-pentoxystyrene,
p-t-pentoxystyrene, o-n-hexoxystyrene, m-n-hexoxystyrene,
p-n-hexoxystyrene, o-2-methylpentoxystyrene,
m-2-methylpentoxystyrene, p-2-methylpentoxystyrene,
o-3-methylpentoxystyrene, m-3-methylpentoxystyrene,
p-3-methylpentoxystyrene, o-1-methylpentoxystyrene,
m-1-methylpentoxystyrene, p-1-methylpentoxystyrene,
o-2,2-dimethylbutoxystyrene, m-2,2-dimethylbutoxystyrene,
p-2,2-dimethylbutoxystyrene, o-2,3-dimethylbutoxystyrene,
m-2,3-dimethylbutoxystyrene, p-2,3-dimethylbutoxystyrene,
o-2,4-dimethylbutoxystyrene, m-2,4-dimethylbutoxystyrene,
p-2,4-dimethylbutoxystyrene, o-3,3-dimethylbutoxystyrene,
m-3,3-dimethylbutoxystyrene, p-3,3-dimethylbutoxystyrene,
o-3,4-dimethylbutoxystyrene, m-3,4-dimethylbutoxystyrene,
p-3,4-dimethylbutoxystyrene, o-4,4-dimethylbutoxystyrene,
m-4,4-dimethylbutoxystyrene, p-4,4-dimethylbutoxystyrene,
o-2-ethylbutoxystyrene, m-2-ethylbutoxystyrene,
p-2-ethylbutoxystyrene, o-1-ethylbutoxystyrene,
m-1-ethylbutoxystyrene, p-1-ethylbutoxystyrene,
o-cyclohexoxystyrene, m-cyclohexoxystyrene, p-cyclohexoxystyrene,
o-phenoxystyrene, m-phenoxystyrene, p-phenoxystyrene, and the like.
Those listed hereinbefore are simply examples, and
nucleus-substituted alkoxystyrenes are not limited thereto. These
may be used singly or in combination with two or more.
[0069] The polymer (C) for use in the resin composition (a) is a
polymer comprising a monomer copolymerizable with styrene or a
styrene derivative. Monomers copolymerizable with styrene or a
styrene derivative for use in the polymer (C) include, for example,
styrene, nucleu-stubstituted alkylstyrenes, nucleus-substituted
aromatic styrenes, .alpha.-substituted alkylstyrenes,
.beta.-substituted alkylstyrenes, nucleus-substituted
alkoxystyrenes, alkyl vinyl ethers, aromatic vinyl ethers,
isobutene, diisobutylene, (meth)acrylic esters having 1 to 8 carbon
atoms, and the like. These may be used singly or in combination
with two or more.
[0070] Nucleus-substituted alkylstyrenes, nucleus-substituted
aromatic styrenes, .alpha.-substituted alkylstyrenes,
.beta.-substituted alkylstyrenes, and nucleus-substituted
alkoxystyrenes include the same as listed for the monomers for use
in the polymer (B).
[0071] Alkyl groups in alkyl vinyl ethers are not particularly
limited, and any alyl group may be employed. Alkyl vinyl ethers
include, for example, those having alkyl groups such as methyl,
ethyl, propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 2-methylbutyl,
3-methylbutyl, t-pentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl,
4-methylpentyl, 1-methylpentyl, 2,2-dimethylbutyl,
2,3-dimethylbutyl, 2,4-dimethylbutyl, 3,3-dimethylbutyl,
3,4-dimethylbutyl, 4,4-dimethylbutyl, 2-ethylbutyl, 1-ethylbutyl,
cyclohexyl, and the like. Those listed hereinbefore are simply
examples, and alkyl vinyl ethers are not limited thereto. These may
be used singly or in combination with two or more.
[0072] Aromatic vinyl ethers include, for example, phenyl vinyl
ether and the like. Those listed hereinbefore are simply examples,
and aromatic vinyl ethers are not limited thereto.
[0073] (Meth)acrylic esters having 1 to 8 carbon atoms include
methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate,
n-butyl (meth)acrylate, i-butyl (meth)acrylate, n-pentyl
(meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate,
n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like.
Those listed hereinbefore are simply examples, and (meth)acrylic
esters having 1 to 8 carbon atoms are not limited thereto. These
may be used singly or in combination with two or more.
[0074] The above styrene, nucleus-substituted alkylstyrenes,
.alpha.-substituted alkylstyrenes, .beta.-substituted
alkylstyrenes, nucleus-substituted alkoxystyrenes, alkyl vinyl
ethers, aromatic vinyl ethers, isobutene, diisobutylene,
(meth)acrylic esters having 1 to 8 carbon atoms, and the like for
use in the polymer (C) may have a substituent such as an alkyl
group, a phenyl group, a halogen atom and the like at an optional
position.
[0075] Methods of the production of the above polymers (A), (B) and
(C) in the resin composition (a) of the present invention are not
particularly limited, and the polymers can be produced by a
conventional method. For example, they can be produced by cationic
polymerization, anionic polymerization, radical polymerization,
living radical polymerization, or the like. The above
polymerization methods can be selected depending on a catalyst
employed.
[0076] Catalysts for use in cationic polymerization are not
particularly limited, and publicly known catalysts may be employed.
Such catalysts that may be employed include, for example, Lewis
acids such as aluminium chloride, iron chloride, tin chloride, zinc
chloride, strontium chloride, scandium chloride and the like,
proton acids such as sulfuric acid, para-toluenesulfonic acid,
hydrochloric acid, nitric acid and the like, alkylaluminium
chlorides, and the like. Those listed hereinbefore are simply
examples, and the catalysts are not limited thereto. These may be
used singly or in combination with two or more.
[0077] Catalysts for use in anionic polymerization are not
particularly limited, and publicly known catalysts may be employed.
Such catalysts that may be employed include, for example, butyl
lithium and the like. Those listed hereinbefore are simply
examples, and the catalysts are not limited thereto.
[0078] Catalysts for use in radical polymerization are not
particularly limited, and publicly known catalysts may be employed.
Such catalysts include, for example, peroxides such as benzoyl
peroxide, lauryl peroxide, methyl ethyl ketone peroxide and the
like. Those listed hereinbefore are simply examples, and the
catalysts are not limited thereto. These may be used singly or in
combination with two or more.
[0079] Catalysts for use in living radical polymerization are not
particularly limited, and publicly known catalysts may be employed
such catalysts include, for example, a combined system of benzoyl
peroxide and a nitroxide compound, a combined system of a Ru
complex/an alkoxyaluminum and the like. Those listed hereinbefore
are simply examples, and the catalysts are not limited thereto.
These may be used singly or in combination with two or more.
[0080] With respect to polymerization methods, the polymers can be
synthesized by solution polymerization, suspension polymerization,
bulk polymerization, or the like. In particular, the solution
polymerization method is the most preferable.
[0081] Solvents employed are not particularly limited, and publicly
known solvents may be employed. Typical solvents include, for
example, chloromethane, dichloromethane, trichloromethane,
tetrachloromethane, chloroethane, dichloroethane, trichloroethane,
tetrachloroethane, chloroethylene, dichloroethylene, nitrobenzene,
dinitrobenzene, trinitrobenzene, alkylbenzenes such as
methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene,
diethylbenzene, triethylbenzene and the like, ketones such as
acetone, methyl ethyl ketone, methyl isobutyl ketone and the like,
and esters such as MMA, ethyl acetate, butyl acetate and the like.
Those listed hereinbefore are simply examples, and the solvents are
not limited thereto. These may be used singly or in combination
with two or more.
[0082] The polymerization temperature is preferably in the range of
-100 to 180.degree. C. If the polymerization reaction is carried
out at a lower temperature than -100.degree. C., decrease in
reactivity is caused, so that it is difficult to obtain a
sufficiently high molecular weight compound. The temperatures
exceeding 180.degree. C. lead to too high reactivity of the
propagation terminal, so that it sometimes becomes to be difficult
to obtain a high molecular weight compound because a vast number of
chain transfer reactions occur.
[0083] In the resin composition (a), the weight-average molecular
weight of the polymer (A) is preferably lower than 80000, more
preferably lower than 40000. If the weight-average molecular weight
of the polymer (A) is lower than 80000, fluidity and transparency
of the resin composition (a) tend to decrease.
[0084] To make the weight-average molecular weight of the polymer
(A) within the above range, the molecular weight can be adjusted by
selecting the kind or amount of the catalyst used in
polymerization, using a polymerization inhibitor, using a chain
transfer agent, controlling the polymerization temperature or the
like.
[0085] Furthermore, the weight-average molecular weight (s) of the
polymer (B) and/or the polymer (C) are/is preferably 50000 or
higher, more preferably 100000 or higher. If the weight-average
molecular weight(s) of the polymer (3) and/or the polymer (C)
are/is lower than 50000, strength of a molding material tends to
decrease.
[0086] To make the weight-average molecular weight(s) of the
polymer (B) and/or the polymer (C) within the above range, the
molecular weight(s) can be adjusted by selecting the kind or amount
of the catalyst used in polymerization, using a polymerization
inhibitor, using a chain transfer agent, controlling the
polymerization temperature or the like.
[0087] Weight-average molecular weights can be determined by GPC
measurement with a tetrahydrofuran solution.
[0088] The polymers (A), (B) and (C) obtained by the above method
can be used for the resin composition (a) after isolating the
polymers by a conventional method.
[0089] In the present invention, the content of the polymer (A) is
preferably 30 to 90% by weight of the total of the resin
composition (a), more preferably 50 to 90% by weight, still more
preferably 60 to 85% by weight. If the content of the polymer (A)
is less than 30% by weight or more than 90% by weight of the total
of the resin composition (a), the absolute value of birefringence
tends to increase.
[0090] Moreover, it is preferred to add a diphenylsilicone (D)
and/or a phenolic antioxidant (E) to the resin composition (a).
[0091] Viscosity of the diphenylsilicone (D) for use in the resin
composition (a) of the present invention is not particularly
limited, and any diphenylsilicone (D) having any viscosity may be
used. The addition amount of the diphenylsilicone (D) is preferably
in the range of 0.01 to 1.0% by weight, more preferably 0.05 to
0.8% by weight of the total of the resin composition (a). If the
addition amount is less than 0.01% by weight, the effect on mold
release characteristics from a die in injection molding tends to
decrease, while if the addition amount exceeds 1.0% by weight, heat
resistance tends to decrease.
[0092] Phenolic antioxidants (E) for use in the present invention
include, for example, dibutylhydroxytoluene, alkylated phenols,
4,4'-thiobis(6-t-butyl-3-methylphenol),
4,4'-butylidenebis(6-t-butyl-3-me- thylphenol),
2,2"-methylenebis(4-methyl-6-t-butylphenol),
2,2"-methylenebis(4-ethyl-6-t-butylphenol),
2,6-di-t-butyl-4-ethylphenol,
1,1,-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,
n-octadecyl-3-(4-hydroxy-3,5-t-dibutylphenyl)propionate,
tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
dilaurylthiodipropionate, distearylthiodipropionate,
dimyristylthiodipropionate, and the like, and the phenolic
antioxidants are not limited thereto. These may be used singly or
in combination with two or more. The addition amount of a phenolic
antioxidant (E) is preferably in the range of 0.1 to 3.0% by
weight, more preferably 0.5 to 2.0% by weight of the total of the
resin composition (a). If the addition amount is less than 0.1% by
weight, the effect to suppress changes in hue is a little, while if
the addition amount exceeds 3.0% by weight, transparency and heat
resistance of the resin tend to decrease.
[0093] Methods of mixing the polymers (A), and (B) and/or (C), a
diphenylsilicone (D), and a phenolic antioxidant (E) are not
particularly limited, and a resin composition can be produced by
weighing out prescribed amounts of each polymer and a
diphenylsilicone and a phenolic antioxidant, and melt-kneading
these, or also can be produced by dissolving each polymer, a
diphenylsilicone and a phenolic antioxidant in a solvent such as
toluene, THF, NMP and the like, and then removing the solvent.
[0094] The resin composition (a) of the present invention obtained
as mentioned above preferably has a saturated water absorption of
0.4% or less, and preferably has a birefringence in stretching the
resin composition by 200% in the range of -2.times.10.sup.-6 to
2.times.10.sup.-6. More preferable saturated water absorption is
0.2% or less, and more preferable birefringence in stretching the
resin composition by 200% is in the range of -1.times.10.sup.-6 to
1.times.10.sup.-6.
[0095] Saturated water absorptions exceeding 0.4% lead to an
increased change in refraction index in absorbing water, thus it is
not preferable. Moreover, if the birefringence in stretching the
resin composition by 200% is out of the range of -2.times.10.sup.-6
to 2.times.10.sup.-6, it is not preferable because linearly
polarized light sometimes greatly changes to elliptically polarized
light.
[0096] To make the saturated water absorption within the above
range, it is satisfactory to make the content of the polymer (A)
within the range of 30 to 90% by weight of the total of the resin
composition (a).
[0097] To make the birefringence in stretching the resin
composition by 200% within the above range, it is satisfactory to
make the content of the polymer (A) within the range of 30 to 90%
by weight of the total of the resin composition (a).
[0098] The saturated water absorption (%) in the present invention
can be calculated by measuring the water absorption when the water
absorption reaches saturation with a sample fragment soaked in hot
water at 70.degree. C. "When the water absorption reaches
saturation" is the state in which there is no more change in the
water absorption even if the sample fragment is allowed to be
soaked in hot water at 70.degree. C. for a longer time.
[0099] Furthermore, concerning birefringence, the birefringence in
stretching an obtained molding material by 200% at a temperature
5.degree. C. lower than the glass transition point of the material
can be measured by using, for example, Ellipsometer AEP-100 Type
(produced by Shimadzu Corporation). Measurement conditions are as
follows: temperature; 25.degree. C.; and wavelength of the laser
light: 632.8 nm. Moreover, the glass transition point of a molding
material can be measured as follows. The glass transition point can
be measured by DSC (differential scanning calorimetry). A
measurement by DSC is carried out under a condition of a
temperature-elevating rate of 10.degree. C./min.
[0100] <2> The Resin Composition (b) of the Present
Invention
[0101] A resin composition (b) of the present invention is a resin
composition comprising the following polymers (F), (G) and (H):
[0102] (F) a polymer comprising one or more kinds of indene and
indene derivatives represented by the above general formula
(I);
[0103] (G) a polymer comprising polystyrene or a polystyrene
derivative; and
[0104] (H) a graft polymer having a structure where a polymer
comprising at least one kind of indene and an indene derivative
represented by the general formula (I) bonds to a side chain of a
polymer comprising a monomer copolymerizable with styrene or a
styrene derivative.
[0105] The polymer (F) for use in the resin composition (b) can be
produced in the same manner as the polymer (A) for use in the resin
composition (a) by using the same indene monomers as in the polymer
(A). The weight-average molecular weight of the polymer (F) is
preferably 4000 or higher, more preferably 8000 or higher. If the
weight-average molecular weight of the polymer (F) is lower than
4000, heat resistance tends to decrease.
[0106] To make the weight-average molecular weight of the polymer
(F) within the above range, the molecular weight can be adjusted by
selecting the kind or amount of the catalyst used in
polymerization, using a polymerization inhibitor, using a chain
transfer agent, controlling the polymerization temperature or the
like.
[0107] Furthermore, the polymer (G) for use in the resin
composition (b) can be produced in the same manner as the polymer
(B) for use in the resin composition (a) by using the same styrene
monomers as in the polymer (B).
[0108] The graft polymer (H) for use in the resin composition (b)
has a structure where a polymer comprising one or more kinds of
indene and indene derivatives represented by the general formula
(I) bonds to a side chain of a polymer comprising styrene or a
styrene derivative. That is, the graft polymer (H) has a backbone
unit of the polymer comprising styrene or a styrene derivative and
branch units of the polymer comprising one or more kinds of indene
and indene derivatives represented by the general formula (I).
[0109] Monomers copolymerizable with styrene or a styrene
derivative for use in a constitutional monomer of the backbone unit
of the graft polymer (H) include, for example, styrene,
nucleus-substituted alkylstyrenes, nucleus-substituted aromatic
styrenes, .alpha.-substituted alkylstyrenes, .beta.-substituted
alkylstyrenes, nucleus-substituted alkoxystyrenes, alkyl vinyl
ethers, aromatic vinyl ethers, isobutene, diisobutylene,
(meth)acrylic esters having 1 to 8 carbon atoms, and the like.
[0110] Nucleus-substituted alkylstyrenes, nucleus-substituted
aromatic styrenes, .alpha.-substituted alkylstyrenes,
.beta.-substituted alkylstyrenes, and nucleus-substituted
alkoxystyrenes include the same as listed for the monomers for use
in the polymer (B) of the resin composition (a). Furthermore, alkyl
vinyl ethers, aromatic vinyl ethers, and (meth)acrylic esters
having 1 to 8 carbon atoms include the same as listed for the
monomers for use in the polymer (C) of the resin composition
(a)
[0111] The above styrene, nucleus-substituted alkylstyrenes,
.alpha.-substituted alkylstyrenes, .beta.-substituted
alkylstyrenes, nucleus-substituted alkoxystyrenes, alkyl vinyl
ethers, aromatic vinyl ethers, isobutene, diisobutylene,
(meth)acrylic esters having 1 to 8 carbon atoms, and the like for
use in the graft polymer (H) may have a substituent such as an
alkyl group, a benzene ring, a halogen atom at an optional
position.
[0112] Indene or indene derivatives for use in a constitutional
monomer of a branched unit of the graft polymer (H) include those
represented by the general formula (I) as mentioned above.
[0113] In the resin composition (b) of the present invention,
methods for the production of the above graft polymer (H) include
conventional methods for the production of a graft polymer, and,
for example, there is a method as follows.
[0114] The method comprises dissolving a polymer which was produced
beforehand by radical polymerization of a monomer copolymerizable
with styrene or a styrene derivative, etc., in toluene, THF, NMP or
the like, further dissolving indene or an indene derivative
represented by the general formula (I), thereafter adding a Lewis
acid such as tin chloride, aluminum chloride and the like as a
catalyst and 2,6-bis(t-butyl)pyridine and the like as an assist
catalyst, and conducting cationic polymerization.
[0115] Furthermore, the weight-average molecular weight of the
backbone unit of the graft polymer (H) is preferably 10000 or
higher.
[0116] Furthermore, the weight-average molecular weights of the
polymer (G) and the graft polymer (H) are preferably 50000 or
higher, more preferably 100000 or higher. If the weight-average
molecular weights of the polymer (G) and the graft polymer (H) are
lower than 50000, strength of a molding material tends to
decrease.
[0117] To make the weight-average molecular weights of the polymer
(G) and the graft polymer (H) within the above range, the molecular
weight can be adjusted by selecting the kind or amount of the
catalyst used in polymerization, using a polymerization inhibitor,
using a chain transfer agent, controlling the polymerization
temperature or the like.
[0118] Moreover, it is preferred to add a diphenylsilicone and/or a
phenolic antioxidant to the resin composition (b).
[0119] Similarly to the diphenylsilicone (D) for use in the resin
composition (a), viscosity of the diphenylsilicone (D) for use in
the resin composition (b) of the present invention is not
particularly limited, and any diphenylsilicone (D) having any
viscosity may be used. The addition amount of the diphenylsilicone
(D) is preferably in the range of 0.01 to 1.0% by weight, more
preferably 0.05 to 0.8% by weight of the total of the resin
composition (b). If the addition amount is less than 0.01% by
weight, the effect on mold release characteristics from a die in
injection molding tends to decrease, while if the addition amount
exceeds 1.0% by weight, heat resistance tends to decrease.
[0120] Phenolic antioxidants for use in the resin composition (b)
of the present invention include phenolic antioxidants (E) for use
in the resin composition (a). The addition amount of a phenolic
antioxidant is not particularly limited, and is preferably in the
range of 0.1 to 3.0% by weight, more preferably 0.5 to 2.0% by
weight of the total of the resin composition (b). If the addition
amount of a phenolic antioxidant (E) is less than 0.1% by weight,
the effect to suppress changes in hue is a little, while if the
addition amount exceeds 3.0% by weight, transparency and heat
resistance of the resin tend to decrease.
[0121] Methods of mixing the polymers (F), (G) and (H) obtained by
the above methods, a diphenylsilicone (D), and a phenolic
antioxidant (E) are not particularly limited, and the same methods
as in the above resin composition (a) may be used.
[0122] In the resin composition (b) of the present invention, the
content of the polymer (F) is preferably 30 to 90% by weight of the
total of the resin composition (b), more preferably 50 to 90% by
weight, still more preferably 60 to 85% by weight. If the content
of the polymer (F) is less than 30% by weight or more than 90% by
weight of the total of the resin composition (b), the absolute
value of birefringence tends to increase.
[0123] The resin composition (b) of the present invention obtained
as, mentioned above preferably has a saturated water absorption of
0.4% or less, and preferably has a birefringence in stretching the
resin composition by 200% in the range of -2.times.10.sup.-6 to
2.times.10.sup.-6. More preferable saturated water absorption is
0.2% or less, and more preferable birefringence in stretching the
resin composition by 200% is in the range of -1.times.10.sup.-5 to
1.times.10.sup.-6.
[0124] Saturated water absorptions exceeding 0.4% lead to an
increased change in refraction index in absorbing water, thus it is
not preferable. Moreover, if the birefringence in stretching the
resin composition by 200% is out of the range of -2.times.10.sup.-6
to 2.times.10.sup.-6, it is not preferable because linearly
polarized light sometimes greatly changes to elliptically polarized
light.
[0125] To make the saturated water absorption within the above
range, it is satisfactory to make the content of the polymer (F)
within the range of 30 to 90% by weight of the total of the resin
composition.
[0126] To make the birefringence in stretching the resin
composition by 200% within the above range, it is satisfactory to
make the content of the polymer (F) within the range of 30 to 90%
by weight of the total of the resin composition.
[0127] <3> The Resin Composition (c) of the Present
Invention
[0128] A resin composition (c) of the present invention is a resin
composition comprising the following polymers (I) and (J),
diphenylsilicone (D), and a phenolic antioxidant (E):
[0129] (I) a polymer comprising one or more kinds of indene and
indene derivatives represented by the above general formula (I),
wherein the polymer has a heterocyclic structure in a side chain
thereof; and
[0130] (J) a polymer comprising styrene or a styrene derivative,
and a monomer copolymerizable with styrene or a styrene derivative,
wherein the polymer has a carboxyl group and/or a phenolic hydroxyl
group in a side chain thereof.
[0131] As indene monomers for use in the polymer (I), the same
indene monomers as in the polymer (A) for use in the resin
composition (a) may be used.
[0132] Methods for introducing a heterocyclic structure into a side
chain of the polymer (I) are not particularly limited, and the
following method is an example.
[0133] [1] After producing a polymer that comprises the above
indene or an indene derivative and has functional groups, the
polymer (I) having a heterocyclic structure in a side chain thereof
is produced by reacting the above produced polymer with a compound
having a heterocyclic structure.
[0134] Specifically, in the case of introducing a heterocyclic
structure into a side chain of the polymer (I), for example, a
copolymer having acid anhydride moieties as functional groups can
be obtained by synthesizing a polymer of the above indene or an
indene derivative and a vinyl monomer having an acid anhydride
moiety, such as maleic anhydride. Then, a heterocyclic structure
can be introduced into a side chain by ring-opening the acid
anhydride moiety of maleic anhydride with an amino group of a
compound having an amino group and a heterocyclic structure, such
as aminopyridine.
[0135] [2] The polymer (I) having a heterocyclic structure in a
side chain thereof is produced by copolymerizing a monomer having a
heterocyclic structure with reaction activity with a monomer
copolymerizable with indene or an indene derivative by a
conventional method.
[0136] Monomers having a heterocyclic structure with reaction
activity for use in the above [2] include, for example, pyridine,
imidazoline, pyrazine, pyrimidine, quinoline, indolizine, acridine,
furan, thiophene, oxazole and the like, each of which has a
polymerizable reactive group. Specifically, vinylpyridine, pyridyl
vinyl ether, pyridylmaleimide and the like may be used, and the
monomers are not limited thereto. Furthermore, these may be used
singly or in combination with two or more.
[0137] In the resin composition (c) of the present invention, the
above polymer (J) comprises a monomer copolymerizable with styrene
or a styrene derivative, and it has a carboxyl group and/or a
phenolic hydroxyl group in a side chain thereof.
[0138] Monomers copolymerizable with styrene or a styrene
derivative for use in the polymer (J) include, for example,
nucleus-substituted alkylstyrenes, nucleus-substituted aromatic
styrenes, .alpha.-substituted alkylstyrenes, .beta.-substituted
alkylstyrenes, nucleus-substituted alkoxystyrenes, alkyl vinyl
ethers, aromatic vinyl ethers, and the like, and specifically
include the same monomers as the styrene monomers for use in the
polymer (B) of the resin composition (a).
[0139] Furthermore, monomers copolymerizable with a styrene
derivative for use in the polymer (J) include, for example,
nucleus-substituted alkylstyrenes, nucleus-substituted aromatic
styrenes, .alpha.-substituted alkylstyrenes, .beta.-substituted
alkylstyrenes, nucleus-substituted alkoxystyrenes, alkyl vinyl
ethers, aromatic vinyl ethers, isobutene, diisobutylene,
(meth)acrylic esters having 1 to 8 carbon atoms, and the like, and
specifically include the same monomers as the monomers for use in
the polymer (C) of the resin composition (c).
[0140] Methods for introducing a carboxyl group and/or a phenolic
hydroxyl group into a side chain of the polymer (J) are not
particularly limited, and the following method is an example.
[0141] [1] After producing a polymer that comprises one or more
kinds of the above styrene and styrene derivatives and has
functional groups, the polymer (J) having a carboxyl group and/or a
phenolic hydroxyl group in a side chain thereof is produced by
reacting the above produced polymer with a compound having a
carboxyl group or a phenolic hydroxyl group.
[0142] Specifically, in the case of introducing a carboxyl group
into a side chain of the polymer (J), for example, a copolymer
having alcoholic hydroxyl groups as functional groups can be
obtained by synthesizing a copolymer of the above styrene or
styrene derivative and a vinyl monomer having an alcoholic hydroxyl
group, such as 2-hydroxylethyl methacrylate (HEMA). Then, a
carboxyl group can be introduced into a side chain by conducting a
ring-opening addition of an acid anhydride such as trimellitic
anhydride to an alcoholic hydroxyl group of HEMA.
[0143] Furthermore, in the case of introducing a phenolic hydroxyl
group into a side chain of the polymer (J), a polymer having acid
anhydride moieties as functional groups can be obtained by
synthesizing a polymer of the above styrene or styrene derivative
and a vinyl monomer having an acid anhydride moiety, such as maleic
anhydride. Then, a phenolic hydroxyl group can be introduced into a
side chain by ring-opening the acid anhydride moiety of maleic
anhydride with an amino group of a compound having an amino group
and a phenolic hydroxyl group, such as aminophenol.
[0144] [2] The polymer (J) having a carboxyl group and/or a
phenolic hydroxyl group in a side chain thereof is produced by
copolymerizing a monomer having a carboxyl group or a phenolic
hydroxyl group with reaction activity with the above styrene or
styrene derivatives by a conventional method.
[0145] Monomers having a carboxyl group or a phenolic hydroxyl
group with reaction activity for use in the above [2] include, for
example, methacrylic acid, acrylic acid, maleic acid, vinylphenol,
vinylbenzoic acid and the like, and the monomers are not limited
thereto. Furthermore, these may be used singly or in combination
with two or more.
[0146] In the resin composition (c) of the present invention, the
content of the heterocyclic structure in the polymer (I) is 0.01 to
5 mol % of the total of the resin composition (c), more preferably
0.02 to 2 mol %. If the content of the heterocyclic structure is
less than 0.01 mol %, transparency of the resin composition (c)
tends to decrease, while if the content exceeds 5 mol %, water
absorption of the resin composition tends to increase.
[0147] The content(s) of the carboxyl group and/or the phenolic
hydroxyl group in the polymer (J) are/is 0.01 to 5 mol % of the
total of the resin composition (c), more preferably 0.02 to 2 mol
%. If the content(s) of the carboxyl group and/or the phenolic
hydroxyl group in the polymer (J) are/is less than 0.01 mol %,
transparency of the resin composition (c) tends to decrease, while
if the content exceeds 5 mol %, water absorption of the resin
composition (c) tends to increase.
[0148] In the present invention, the molar ratio of the
heterocyclic structure to the carboxyl group and/or the phenolic
hydroxyl group is preferably 0.1 to 10.0. If this ratio is less
than 0.1 or exceeds 10.0, transparency of the resin composition (c)
tends to decrease.
[0149] Methods of the production of the above polymers (I) and (J)
are not particularly limited in the present invention, and the
polymers can be produced by a conventional method using the
above-mentioned monomers.
[0150] Similarly to the diphenylsilicone (D) for use in the resin
composition (a), viscosity of the diphenylsilicone (D) for use in
the resin composition (C) of the present invention is not
particularly limited, and any diphenylsilicone (D) having any
viscosity may be used. The addition amount of the diphenylsilicone
(D) is preferably in the range of 0.01 to 1.0% by weight, more
preferably 0.05 to 0.8% by weight of the total of the resin
composition (c). If the addition amount is less than 0.01% by
weight, the effect on mold release characteristics from a die in
injection molding tends to decrease, while if the addition amount
exceeds 1.0% by weight, heat resistance tends to decrease.
[0151] Phenolic antioxidants for use in the resin composition (c)
of the present invention include phenolic antioxidants (E) for use
in the resin composition (a). The addition amount of a phenolic
antioxidant is not particularly limited, and is preferably in the
range of 0.1 to 3.0% by weight, more preferably 0.5 to 2.0% by
weight of the total of the resin composition (c). If the addition
amount of a phenolic antioxidant (E) is less than 0.1% by weight,
the effect to suppress changes in hue is a little, while if the
addition amount exceeds 3.0% by weight, transparency and heat
resistance of the resin tend to decrease.
[0152] Methods of mixing the polymers (I) and (J) obtained by the
above methods, a diphenylsilicone (D), and a phenolic antioxidant
(E) are not particularly limited, and the same methods as in the
above resin composition (a) may be used.
[0153] In the resin composition (c) of the present invention, the
content of the polymer (I) is preferably 30 to 90% by weight of the
total of the resin composition (c), more preferably 50 to 90% by
weight, still more preferably 60 to 85% by weight. If the content
of the polymer (I) is less than 30% by weight or more than 90% by
weight of the total of the resin composition (c), the absolute
value of birefringence tends to increase.
[0154] The resin composition (c) of the present invention obtained
as mentioned above preferably has a saturated water absorption of
0.4% or less, and preferably has a birefringence in stretching the
resin composition by 200% in the range of -2.times.10.sup.-6 to
2.times.10.sup.-6. More preferable saturated water absorption is
0.2% or less, and more preferable birefringence in stretching the
resin composition by 200% is in the range of -1.times.10.sup.-6 to
1.times.10.sup.-6.
[0155] Saturated water absorptions exceeding 0.4% lead to an
increased change in refraction index in absorbing water, thus it is
not preferable. Moreover, if the birefringence in stretching the
resin composition by 200% is out of the range of -2.times.10.sup.-6
to 2.times.10.sup.-6, it is not preferable because linearly
polarized light sometimes greatly changes to elliptically polarized
light.
[0156] To make the saturated water absorption within the above
range, it is satisfactory that each of the content(s) of the
carboxyl group and/or the phenolic hydroxyl group in the polymer
(I) and the content(s) of the heterocyclic structure and/or the
alkylamino group in the polymer (J) satisfies the range of 0.005 to
5 mol %.
[0157] To make the birefringence in stretching the resin
composition by 200% within the above range, it is satisfactory to
make the content of the polymer (I) within the range of 30 to 90%
by weight of the total of the resin composition (c)
[0158] <4> The Molding Material of the Present Invention
[0159] The above resin composition (a), resin composition (b) and
resin composition (c) according to the present invention can be
processed to obtain a molding material, a sheet or a film. In the
present invention, optional components may be added when required
in making these resin compositions into molding materials.
[0160] The resin compositions of the present invention may be
applied to semiconductor-related materials that can satisfy the
characteristics such as low permittivity, low hygroscopicity and
high heat resistance, or to optical parts, as well as paints,
photosensitive materials, adhesives, sewage disposal agents, heavy
metal collectors, ion-exchange resins, antistatic agents,
antioxidants, anti-fog agents, anti-corrosive agents, reverse
printing agents, anti-microbial agents, insecticides, medical
materials, coagulants, surfactants, lubricants, binders for solid
fuel, conductivity imparting agents, and the like.
[0161] Optical parts using a molding material of the present
invention include pickup lenses for CD, pickup lenses for DVD,
lenses for facsimile, lenses for LBP, polygonmirrors, prisms, and
the like.
BEST MODE FOR CARRYING OUT THE INVENTION
[0162] The present invention is described in further detail with
reference to some examples. However, the present invention should
not be construed as being limited to these examples.
[0163] Evaluation methods used in the examples are as follows.
[0164] (1) Weight-average Molecular Weight
[0165] The weight-average molecular weight of a polymer synthesized
was determined by GPC measurement with a tetrahydrofuran
solution.
[0166] (2) Fluidity (MI)
[0167] The fluidity of a resin composition was determined by
measuring a melt flow rate at 220.degree. C. with a load of 5
kgf.
[0168] (3) Saturated Water Absorption
[0169] The saturated water absorption of a sample was determined by
measuring the water absorption when the water absorption reaches
saturation with a sample soaked in hot water at 70.degree. C. Water
absorption in Table 1 shows the saturated water absorption.
[0170] (4) Heat Resistance (Tg)
[0171] The heat resistance was evaluated by measuring the glass
transition point by DSC (differential scanning calorimetry). The
measurement of DSC was carried out under a condition of a rate of
temperature rise of 10.degree. C./min.
[0172] (5) Relative Permittivity
[0173] The relative permittivity was measured by using precision
LCR meter 4284A Type produced by Hewlett-Packard Company under
conditions of 20 kV, 1 kHz and 25.degree. C.
[0174] (6) Bending Strength
[0175] The bending strength of a sample fragment was measured by
using AGS-1000G produced by Shimadzu Corporation. The test was
carried out at room temperature under conditions of a test speed of
0.5 mm/min., a span of 20 mm and the width of the sample fragment
of 10 mm.
[0176] (7) Transparency
[0177] The transparency of a formed sample was measured by using
V-570produced by JASCO Corporation at25.degree. C. The transparency
measured at measurement wavelengths in the range of 400 to 800 nm
was assumed to be the total light ray transparency.
[0178] (8) Birefringence
[0179] The birefringence of an obtained molding material stretched
by 150% at a temperature 5.degree. C. lower than the glass
transition temperature of the material was measured. The
measurement was carried out by using Ellipsometer AEP-100 Type
produced by Shimadzu Corporation at 25.degree. C. The wavelength of
the laser beam was 632.8 nm.
[0180] (9) Change in Hue
[0181] After a resin was allowed to abide in an injection molding
machine at 250.degree. C. for 30 minutes, injection molding was
carried out, and then the change in hue of the molding product thus
obtained was measured with a spectrocolormeter (produced by Sakata
Ink Corporation, Macbeth color-eye 7000A).
[0182] (10) Mold Release Characteristics
[0183] With respect to the mold release characteristics in
injection molding, injection molding of a resin was actually
carried out, and the surface condition of the resin mold-released
from a die and whether the resin was broken or not were visually
confirmed.
EXAMPLE 1
[0184] Placed in a 100-mL flask were 10.0 g of indene and 30.0 g of
toluene, and 0.05 g of FeCl.sub.3was added thereto at 25.degree.
C., thereby being allowed to react for 12 hours. Thereafter, 0.05 g
of methanol was added to this reaction mixture liquid, and then the
liquid was stirred to obtain a homogeneous solution. The
homogeneous solution thus obtained was gradually added to 100 g of
methanol to obtain 9.7 g of a white precipitate. This white
precipitate was dried under reduced pressure to obtain a polymer
(A). The weight-average molecular weight of this polymer was
2200.
[0185] Placed in a 100-mL flask were 20.0 g of styrene and 0.1 g of
benzoyl peroxide, and the mixture was stirred to dissolve. Then, 60
g of distilled water and 0.01 g of calcium phosphate were added
thereto, and the mixture was allowed to react at 70.degree. C. for
12 hours with being stirred. A granular polymer thus obtained was
isolated and washed with hydrochloric acid. Subsequently, the
polymer was dried at 50.degree. C. for about 2 hours to obtain a
polymer (B). The weight-average molecular weight of the polymer
obtained was 200000.
[0186] Dissolved in 20 g of toluene were 6.0 g of the polymer (A)
and 4.0 g of the polymer (B), and the mixture was added to about
300 g of methanol to precipitate a solid. This solid was dried at
40.degree. C. for 6 hours to obtain a desired white precipitate.
This resin composition was hot-pressed to produce a molding
material having a thickness of 2 mm. This molding material was used
as a sample fragment. The above-mentioned evaluations were carried
out using this sample fragment. The evaluation results are shown in
Table 1.
EXAMPLE 2
[0187] Placed in a 100-mL flask were 8.0 g of indene, 2.0 g of
4-methylstyrene and 30.0 g of methylene chloride, and 0.05 g of
FeCl.sub.3 was added thereto at -40.degree. C., thereby being
allowed to react for 12 hours. Thereafter 0.05 g of methanol was
added to this reaction mixture liquid, and then the liquid was
stirred to obtain a homogeneous solution. The homogeneous solution
thus obtained was gradually added to 100 g of methanol to obtain
9.8 g of a white precipitate. This white precipitate was dried
under reduced pressure to obtain a polymer (A). The weight-average
molecular weight of this polymer was 15000.
[0188] Placed in a 100-mL flask were 20.0 g of styrene and 0.1 g of
benzoyl peroxide, and the mixture was stirred to dissolve. Then, 60
g of distilled water and 0.01 g of calcium phosphate were added
thereto, and the mixture was allowed to react at 70.degree. C. for
12 hours with being stirred. After reaction was allowed for a
predetermined time, a granular polymer was isolated and washed with
hydrochloric acid. Subsequently, the polymer was dried at
50.degree. C. for about 2 hours to obtain a polymer (B). The
weight-average molecular weight of the polymer obtained was
200000.
[0189] Placed in a 100-mL flask were 14.0 g of styrene, 5.0 g of
4-methylstyrene, 1.0 g of butyl acrylate and 0.1 g of benzoyl
peroxide, and the mixture was stirred to dissolve. Then, 60 g of
distilled water and 0.01 g of calcium phosphate were added thereto,
and the mixture was allowed to react at 70.degree. C. for 12 hours
with being stirred. The reaction was allowed for a predetermined
time. A granular polymer thus obtained was isolated and washed with
hydrochloric acid. Subsequently, the polymer was dried at
50.degree. C. for about 2 hours to obtain a polymer (C). The
weight-average molecular weight of the polymer obtained was
240000.
[0190] Dissolved in 20 g of toluene were 6.0 g of the polymer (A),
1.5 g of the polymer (B) and 2.5 g of the polymer (C), and the
mixture was added to about 300 g of methanol to precipitate a
solid. This solid was dried at 40.degree. C. for 6 hours to obtain
a desired white precipitate. This resin composition was hot-pressed
to produce a molding material having a thickness of 2 mm. This
molding material was used as a sample fragment. The evaluation
results obtained by evaluating this sample fragment in the same
manner as in Example 1 are shown in Table 1.
EXAMPLE 3
[0191] Placed in a 100-mL flask were 10.0 g of indene and 30.0 g of
toluene, and 0.05 g of FeCl.sub.3was added thereto at 25.degree.
C., thereby being allowed to react for 12 hours. Thereafter 0.05 g
of methanol was added to this reaction mixture liquid, and then the
liquid was stirred to obtain a homogeneous solution. The
homogeneous solution thus obtained was gradually added to 100 g of
methanol to obtain 9.7 g of a white precipitate. This white
precipitate was dried under reduced pressure to obtain a polymer
(A). The weight-average molecular weight of this polymer was
2200.
[0192] Placed in a 100-mL flask were 20.0 g of styrene and 0.1 g of
benzoyl peroxide, and the mixture was stirred to dissolve. Then, 60
g of distilled water and 0.01 g of calcium phosphate were added
thereto, and the mixture was allowed to react at 70.degree. C. for
12 hours with being stirred. A granular polymer thus obtained was
isolated and washed with hydrochloric acid. Subsequently, the
polymer was dried at 50.degree. C. for about 2 hours to obtain a
polymer (B). The weight-average molecular weight of the polymer
obtained was 200000.
[0193] Dissolved in 20 g of toluene were 6.0 g of the polymer (A)
and 4.0 g of the polymer (B), 0.01 g of diphenylsilicone (produced
by Shin-Etsu Chemical Co., Ltd.) having a viscosity of 500 CS and
0.05 g of n-octadecyl-3-(4-hydroxy-3,5-t-dibutylphenyl)propionate,
and the mixture was added to about 300 g of methanol to precipitate
a solid. This solid was dried at 40.degree. C. for 6 hours to
obtain a desired resin composition. This resin composition was
hot-pressed to produce a molding material having a thickness of 2
mm. This molding material was used as a sample fragment. The
above-mentioned evaluations were carried out using this sample
fragment. The evaluation results are shown in Table 1.
EXAMPLE 4
[0194] Placed in a 100-mL flask were 8.0 g of indene, 2.0 g of
4-methylstyrene and 30.0 g of methylene chloride, and 0.05 g of
FeCl.sub.3 was added thereto at -40.degree. C., thereby being
allowed to react for 12 hours. Thereafter, 0.05 g of methanol was
added to this reaction mixture liquid, and then the liquid was
stirred to obtain a homogeneous solution. The homogeneous solution
thus obtained was gradually added to 100 g of methanol to obtain
9.8 g of a white precipitate. This white precipitate was dried
under reduced pressure to obtain a polymer (A). The weight-average
molecular weight of this polymer was 15000.
[0195] Placed in a 100-mL flask were 20.0 g of styrene and 0.1 g of
benzoyl peroxide, and the mixture was stirred to dissolve. Then, 60
g of distilled water and 0.01 g of calcium phosphate were added
thereto, and the mixture was allowed to react at 70.degree. C. for
12 hours with being stirred. A granular polymer thus obtained was
isolated and washed with hydrochloric acid. Subsequently, the
polymer was dried at 50.degree. C. for about 2 hours to obtain a
polymer (B). The weight-average molecular weight of the polymer
obtained was 200000.
[0196] Placed in a 100-mL flask were 14.0 g of styrene, 5.0 g of
4-methylstyrene, 1.0 g of butyl acrylate and 0.1 g of benzoyl
peroxide, and the mixture was stirred to dissolve. Then, 60 g of
distilled water and 0.01 g of calcium phosphate were added thereto,
and the mixture was allowed to react at 70.degree. C. for 12 hours
with stirring. A granular polymer thus obtained was isolated and
washed with hydrochloric acid. Subsequently, the polymer was dried
at 50.degree. C. for about 2 hours to obtain a polymer (B). The
weight-average molecular weight of the polymer obtained was
240000.
[0197] Dissolved in 20 g of toluene were 6.0 g of the polymer (A),
1.5 g of the polymer (B), 2.5 g of the polymer (C), 0. 01 g of
diphenylsilicone having a viscosity of 500 CS and 0.05 g of
n-octadecyl-3-(4-hydroxy-3,5-t- -dibutylphenyl) propionate, and the
mixture was added to about300 g of methanol to precipitate a solid.
This solid was dried at 40.degree. C. for 6 hours to obtain a
desired resin composition. This resin composition was hot-pressed
to produce a molding material having a thickness of 2 mm. This
molding material was used as a sample fragment. The above-mentioned
evaluations were carried out using this sample fragment. The
evaluation results are shown in Table 1.
1 TABLE 1 Example 1 Example 2 Example 3 Example 4 Item unit Polymer
A Polymer B Polymer A Polymer B Polymer C Polymer A Polymer B
Polymer A Polymer B Polymer C Molecular g/mol 2200 200000 15000
200000 240000 2200 200000 15000 200000 240000 weight (Mw) Mixing
ratio % by 60 40 60 15 25 60 40 60 15 25 weight Antioxidant E % by
0 0 0.5 0.5 weight Silicone % by 0 0 0.1 0.1 amount D weight
Fluidity (MI) g/10 21 12 21 12 minutes Water % 0.09 0.08 0.09 0.08
absorption Heat .degree. C. 135 142 135 142 resistance (Tg)
Relative -- 2.3 2.2 2.3 2.2 permittivity Bending MPa 80 85 80 85
strength Transparency % 85 85 85 85 Birefringence -- 1 .times.
10.sup.-6 1 .times. 10.sup.-6 1 .times. 10.sup.-6 1 .times.
10.sup.-6 Change in hue -- 0.28 0.29 0.12 0.15
COMPARATIVE EXAMPLE 1
[0198] Placed in a 100-mL flask were 10.0 g of indene and 30.0 g of
toluene, and 0.05 g of FeCl.sub.3was added thereto at 25.degree.
C., thereby being allowed to react for 12 hours. Thereafter, 0.05 g
of methanol was added to this reaction mixture liquid, and then the
liquid was stirred to obtain a homogeneous solution. The
homogeneous solution thus obtained was gradually added to 100 g of
methanol to obtain 9.7 g of a white precipitate. This white
precipitate was dried under reduced pressure to obtain a polymer
(A). The weight-average molecular weight of this polymer was
2200.
[0199] Next, placed in a 100-mL flask were 20.0 g of styrene and
0.1 g of benzoyl peroxide, and the mixture was stirred to dissolve.
Then, 60 g of distilled water and 0.01 g of calcium phosphate were
added thereto, and the mixture was allowed to react at 70.degree.
C. for 12 hours with being stirred. A granular polymer thus
obtained was isolated and washed with hydrochloric acid.
Subsequently, the polymer was dried at 50.degree. C. for about 2
hours to obtain a polymer(B). The weight-average molecular weight
of the polymer obtained was 200000.
[0200] Dissolved in 20 g of toluene were 4.0 g of the polymer (A)
and 6.0 g of the polymer (B), and the mixture was added to about
300 g of methanol to precipitate a solid. This solid was dried at
40.degree. C. for 6 hours to obtain a desired white precipitate.
This resin composition was hot-pressed to produce a molding
material having a thickness of 2 mm. This molding material was used
as a sample fragment. The above-mentioned evaluations were carried
out using this sample fragment. The evaluation results are shown in
Table 2.
COMPARATIVE EXAMPLE 2
[0201] Placed in a 100-mL flask were 10.0 g of indene and 30.0 g of
nitrobenzene, and 0.05 g of FeCl.sub.3 was added thereto at
0.degree. C., thereby being allowed to react for 12 hours.
Thereafter, 0.05 g of methanol was added to this reaction mixture
liquid, and then the liquid was stirred to obtain a homogeneous
solution. The homogeneous solution thus obtained was gradually
added to 100 g of methanol to obtain 9.7 g of a white precipitate.
This white precipitate was dried under reduced pressure to obtain a
polymer (A). The weight-average molecular weight of this polymer
was 7500.
[0202] Next, placed in a 100-mL flask were 20.0 g of styrene and
0.1 g of benzoyl peroxide, and the mixture was stirred to dissolve.
Then, 60 g of distilled water and 0.01 g of calcium phosphate were
added thereto, and the mixture was allowed to react at 70.degree.
C. for 12 hours with being stirred. A granular polymer thus
obtained was isolated and washed with hydrochloric acid.
Subsequently, the polymer was dried at 50.degree. C. for about 2
hours to obtain a polymer (B). The weight-average molecular weight
of the polymer obtained was 200000.
[0203] Dissolved in 20 g of toluene were 9.5 g of the polymer (A)
and 0.5 g of the polymer (B), and the mixture was added to about
300 g of methanol to precipitate a solid. This solid was dried at
40.degree. C. for 6 hours to obtain a white precipitate of a
desired resin composition. This resin composition was hot-pressed
to produce a molding material having a thickness of 2 mm. This
molding material was used as a sample fragment. The above-mentioned
evaluations were carried out using this sample fragment. The
evaluation results are shown in Table 2.
2 TABLE 2 Comparative Example 1 Comparative Example 2 item unit
Polymer A Polymer B Polymer A Polymer B Molecular weight g/mol 2200
200000 7500 200000 (Mw) Mixing ratio % by weight 40 60 95 5
Antioxidant E % by weight 0 0 Silicone amount D % by weight 0 0
Fluidity (MI) g/10 minutes 13 12 Water absorption % 0.10 0.08 Heat
resistance .degree. C. 121 142 (Tg) Relative -- 2.3 2.3
permittivity Bending strength Mpa 80 48 Transparency % 85 85
Birefringence -- 5 .times. 10.sup.-5 Could not be measured Change
in hue -- 0.28 0.29
EXAMPLE 5
[0204] Placed in a 100-mL flask were 10.0 g of indene and 30.0 g of
nitrobenzene, and 0.05 g of FeCl.sub.3 was added thereto at
0.degree. C., thereby being allowed to react for 12 hours.
Thereafter, 0.05 g of methanol was added to this reaction mixture
liquid, and then the liquid was stirred to obtain a homogeneous
solution. The homogeneous solution thus obtained was gradually
added to 100 g of methanol to obtain 9.7 g of a white precipitate.
This white precipitate was dried under reduced pressure to obtain a
polymer (F). The weight-average molecular weight of this polymer
was 7500.
[0205] Placed in a 100-mL flask were 20.0 g of styrene and 0.1 g of
benzoyl peroxide, and the mixture was stirred to dissolve. Then, 60
g of distilled water and 0.01 g of calcium phosphate were added
thereto, and the mixture was allowed to react at 70.degree. C. for
12 hours with being stirred. A granular polymer thus obtained was
isolated and washed with hydrochloric acid. Subsequently, the
polymer was dried at 50.degree. C. for about 2 hours to obtain a
polymer (G). The weight-average molecular weight of the polymer
obtained was 200000.
[0206] In advance, 18.0 g of styrene, 2.0 g of
p-chloromethylstyrene and 0.1 g of benzoyl peroxide were placed in
a 100-mL flask, the mixture was stirred to dissolve. Then, 60 g of
distilled water and 0.1 g of calcium phosphate were added thereto,
and the mixture was allowed to react at 70.degree. C. for 12 hours
with stirring. Thereafter a granular polymer was isolated and
washed with hydrochloric acid. Subsequently, the polymer was dried
at 50.degree. C. for about 2 hours. Dissolved in 30 g of toluene
was 6.0 g of the granular polymer thus obtained, and 4.0 g of
indene was further added thereto, and the mixture was stirred until
the mixture became homogeneoue. After that, 0.003 g of
2,6-bis(t-butyl)pyridine was added at 25.degree. C. and dissolved.
Then, 0.03 g of tin chloride was added, and the mixture was allowed
to stand for 24 hours to obtain a graft polymer (H). After 0.05 g
of methanol was added to the reaction mixture liquid thus obtained,
this reaction mixture liquid was poured in methanol in an amount
about 10 times that of the reaction mixture liquid of methanol, and
a polymer thus formed was isolated. This polymer was dried at
40.degree. C. for 6 hours to obtain 9.8 g of a polymer (H). The
weight-average molecular weight of this polymer was 210000.
[0207] Dissolved in 20 g of toluene were 5.5 g of the polymer (F),
3.5 g of the polymer (G), and 1.0 g of the polymer (H), and the
mixture was added to about 300 g of methanol to precipitate a
solid. This solid was dried at 40.degree. C. for 6 hours to obtain
a white precipitate of a desired resin composition. This resin
composition was hot-pressed to produce a molding material having a
thickness of 2 mm. This molding material was used as a sample
fragment. The above-mentioned evaluations were carried out using
this sample fragment. The evaluation results are shown in Table
3.
EXAMPLE 6
[0208] Placed in a 100-mL flask were 10.0 g of indene and 30.0 g of
nitrobenzene, and 0.05 g of FeCl.sub.3 was added thereto at
0.degree. C., thereby being allowed to react for 12 hours.
Thereafter, 0.05 g of methanol was added to this reaction mixture
liquid, and then the liquid was stirred to obtain a homogeneous
solution. The homogeneous solution thus obtained was gradually
added to 100 g of methanol to obtain 9.7 g of a white precipitate.
This white precipitate was dried under reduced pressure to obtain a
polymer (F). The weight-average molecular weight of this polymer
was 7500.
[0209] Placed in a 100-mL flask were 20.0 g of styrene and 0.1 g of
benzoyl peroxide and the mixture was stirred to dissolve. Then, 60
g of distilled water and 0.01 g of calcium phosphate were added
thereto, and the mixture was allowed to react at 70.degree. C. for
12 hours with being stirred. A granular polymer thus obtained was
isolated and washed with hydrochloric acid. Subsequently, the
polymer was dried at 50.degree. C. for about 2 hours to obtain a
polymer (G). The weight-average molecular weight of the polymer
obtained was 200000.
[0210] In advance, 18.0 g of styrene, 2.0 g of
p-chloromethylstyrene and 0.1 g of benzoyl peroxide were placed in
a 100-mL flask, the mixture was stirred to dissolve. Then, 60 g of
distilled water and 0.1 g of calcium phosphate were added thereto,
and the mixture was allowed to react at 70.degree. C. for 12 hours
with being stirred. After the reaction was allowed for a
predetermined time, the granular polymer was isolated and washed
with hydrochloric acid. Subsequently, the polymer was dried at
50.degree. C. for about 2 hours. Dissolved in 30 g of toluene was
6.0 g of the granular polymer thus obtained, and 4.0 g of indene
was further added thereto, and the mixture was stirred until the
mixture became homogeneous. After that, 0.003 g of
2,6-bis(t-butyl)pyridine was added at 25.degree. C. and dissolved.
Then, 0.03 g of tin chloride was added, and the mixture was allowed
to stand for 24 hours to obtain a graft polymer. After 0.05 g of
methanol was added to the reaction mixture liquid, this reaction
mixture liquid was poured in methanol in about 10 times the amount
of the reaction mixture liquid of methanol, and a polymer thus
formed was isolated. This polymer was dried at 40.degree. C. for 6
hours to obtain 9.8 g of a polymer (H). The weight-average
molecular weight of this polymer was 210000.
[0211] Dissolved in 20 g of toluene were 5.5 g of the polymer (F),
3.5 g of the polymer (G), 1.0 g of the polymer (H), 0.01 g of
diphenylsilicone (produced by Shin-Etsu Chemical Co., Ltd.) having
a viscosity of 500 CS and 0.05 g of
n-octadecyl-3-(4-hydroxy-3,5-t-dibutylphenyl)propionate, and the
mixture was added to about 300 g of methanol to precipitate a
solid. This solid was dried at 40.degree. C. for 6 hours to obtain
a white precipitate of a desired resin composition. This resin
composition was hot-pressed to produce a molding material having a
thickness of 2 mm. This molding material was used as a sample
fragment. The above-mentioned evaluations were carried out using
this sample fragment. The evaluation results are shown in Table
3.
EXAMPLE 7
[0212] Placed in a 100-ml flask were 10.0 g of indene and 30.0 g of
toluene, and 0.01 g of AlCl.sub.3 was added thereto at 25.degree.
C., thereby being allowed to react for 6 hours. Thereafter 0.01 g
of methanol was added to this reaction mixture liquid, and then the
liquid was stirred to obtain a homogeneous solution. The
homogeneous solution thus obtained was gradually added to 100 g of
methanol to obtain 9.8 g of a white precipitate. This white
precipitate was dried under reduced pressure to obtain a polymer
(F). The weight-average molecular weight of this polymer was
10000.
[0213] Placed in a 100-mL flask were 20.0 g of styrene and 0.1 g of
benzoyl peroxide, and the mixture was stirred to dissolve. Then, 60
g of distilled water and 0.01 g of calcium phosphate were added to
the monomer mixture, and the mixture was allowed to react at
70.degree. C. for 12 hours with being stirred. A granular polymer
thus obtained was isolated to obtain a polymer (G). The
weight-average molecular weight of the polymer obtained was
200000.
[0214] In advance, 18.0 g of styrene, 2.0 g of
p-chloromethylstyrene and 0.1 g of benzoyl peroxide were placed in
a 100-mL flask, the mixture was stirred to dissolve. Then, 60 g of
distilled water and 0.01 g of calcium phosphate were added to the
monomer mixture, and the mixture was allowed to react at 70.degree.
C. for 12 hours with bring stirred. The granular polymer thus
obtained was isolated and washed with hydrochloric acid.
Subsequently, the polymer was dried at 50.degree. C. for about 2
hours. Dissolved in 30 g of toluene was 6.0 g of the granular
polymer thus obtained, and 4.0 g of indene was further added
thereto, and the mixture was stirred until the mixture became
homogeneous. After that, 0.003 g of 2,6-bis(t-butyl)pyridine was
added at 25.degree. C. and dissolved. Then, 0.03 g of tin chloride
was added, and the mixture was allowed to stand for 24 hours to
obtain a graft polymer. After 0.05 g of methanol was added to the
reaction mixture liquid thus obtained, this reaction mixture liquid
was poured in methanol in about 10 times the amount of the reaction
mixture liquid of methanol, and a polymer thus formed was isolated.
This polymer was dried at 40.degree. C. for 6 hours to obtain 9.8 g
of a polymer (H). The weight-average molecular weight of this
polymer was 200000.
[0215] Dissolved in 20 g of toluene were 6.0 g of the polymer (F),
3.5 g of the polymer (G), 0.5 g of the polymer (H), 0.01 g of
diphenylsilicone (produced by Shin-Etsu Chemical Co., Ltd.) having
a viscosity of 500 CS and 0.05 g of
n-octadecyl-3-(4-hydroxy-3,5-t-dibutylphenyl)propionate, and the
mixture was added to about 300 g of methanol to precipitate a
solid. This solid was dried at 40.degree. C. for 6 hours to obtain
a desired resin composition. This resin composition was hot-pressed
to produce a molding material having a thickness of 2 mm. This
molding material was used as a sample fragment. The above-mentioned
evaluations were carried out using this sample fragment. The
evaluation results are shown in Table 3.
3 TABLE 3 Example 5 Example 6 Example 7 item unit Polymer F Polymer
G Polymer H Polymer F Polymer G Polymer H Polymer F Polymer G
Polymer H Molecular g/mol 7500 200000 210000 7500 200000 210000
10000 200000 200000 weight (Mw) Mixing ratio % by 55 35 10 55 35 10
60 35 5 weight Antioxidant E % by 0 0.5 0.5 weight Silicone amount
D % by 0 0.1. 0.1 weight Fluidity (MI) g/10 18 18 22 minutes Water
% 0.09 0.09 0.08 absorption Heat resistance .degree. C. 147 147 152
(Tg) Relative -- 2.3 2.3 2.2 permittivity Bending MPa 80 80 80
strength Transparency % 85 85 85 Birefringence -- 1 .times.
10.sup.-6 1 .times. 10.sup.-6 1 .times. 10.sup.-6 Change in hue --
0.35 0.12 0.11
COMPARATIVE EXAMPLE 3
[0216] Placed in a 100-mL flask were 10.0 g of indene and 30.0 g of
nitrobenzene, and 0.05 g of FeCl.sub.3was added thereto at
0.degree. C., thereby being allowed to react for 12 hours.
Thereafter, 0.05 g of methanol was added to this reaction mixture
liquid, and then the liquid was stirred to obtain a homogeneous
solution. The homogeneous solution thus obtained was gradually
added to 100 g of methanol to obtain 9.7 g of a white precipitate.
This white precipitate was dried under reduced pressure to obtain a
polymer (F). The weight-average molecular weight of this polymer
was 7500.
[0217] Placed in a 100-mL flask were 20.0 g of styrene and 0.1 g of
benzoyl peroxide, and the mixture was stirred to dissolve. Then, 60
g of distilled water and 0.01 g of calcium phosphate were added to
the monomer mixture, and the mixture was allowed to react at
70.degree. C. for 12 hours with being stirred. A granular polymer
thus obtained was isolated and washed with hydrochloric acid.
Subsequently, the polymer was dried at 50.degree. C. for about 2
hours to obtain a polymer (G). The weight-average molecular weight
of the polymer obtained was 200000.
[0218] Dissolved in 2.0 g of toluene were 6.0 g of the polymer (E)
and 4.0 g of the polymer (G), and the mixture was added to about
300 g of methanol to precipitate a solid. This solid was dried at
40.degree. C. for 6 hours to obtain a white precipitate of a resin
composition. This resin composition was hot-pressed to produce a
molding material having a thickness of 2 mm. This molding material
was used as a sample fragment. The above-mentioned evaluations were
carried out using this sample fragment. The evaluation results are
shown in Table 4.
4 TABLE 4 Comparative Example 3 item unit Polymer F Polymer G
Molecular weight g/mol 7500 200000 (Mw) Mixing ratio % by weight 60
40 Antioxidant E % by weight 0 Silicone amount D % by weight 0
Fluidity (MI) g/10 minutes 17 Water absorption % 0.10 Heat
resistance (Tg) .degree. C. 142 Relative permittivity -- 2.3
Bending strength MPa 75 Transparency % 55 Birefringence -- Could
not be measured Change in hue -- 0.35
EXAMPLE 8
[0219] Placed in a 100-mL flask were 9.95 g of indene, 0.05 g of
vinylpyridine and 30.0 g of methylene chloride, and 0.01 g of
FeCl.sub.3 was added thereto at -40.degree. C., thereby being
allowed to react for 24 hours. Thereafter, 0.05 g of methanol was
added at room temperature to this reaction mixture liquid, and then
the liquid was stirred to obtain a homogeneous solution. The
homogeneous solution thus obtained was gradually added to 100 g of
methanol to obtain 9.8 g of a white precipitate. This white
precipitate was dried under reduced pressure to obtain a polymer
(I). The weight-average molecular weight of this polymer was
97000.
[0220] Placed in a 100-mL flask were 19.9 g of styrene, 0.1 g of
methacrylic acid and 0.1 g of benzoyl peroxide, and the mixture was
stirred to dissolve. Then, the mixture was sealed and allowed to
react at 70.degree. C. for 12 hours with reflux. The polymer thus
obtained was granulated and then washed with methanol.
Subsequently, the polymer was dried at 50.degree. C. for about 8
hours to obtain a polymer (J). The weight-average molecular weight
of the polymer obtained was 250000.
[0221] Dissolved in 20 g of toluene were 6.0 g of the polymer (I),
4.0 g of the polymer (J), 0.01 g of diphenylsilicone having a
viscosity of 500 CS and 0.05 g of
n-octadecyl-3-(4-hydroxy-3,5-t-dibutylphenyl)propionate, and the
mixture was added to about 300 g of methanol to precipitate a
solid. This solid was dried at 40.degree. C. for 6 hours to obtain
a desired resin composition. This resin composition was hot-pressed
to produce a molding material having a thickness of 2 mm. This
molding material was used as a sample fragment. The above-mentioned
evaluations were carried out using this sample fragment. The
evaluation results are shown in Table 5.
EXAMPLE 9
[0222] Placed in a 100-mL flask were 9.95 g of indene, 0.05 g of
vinylpyridine and 30.0 g of toluene, and 0.01 g of AlCl.sub.3 was
added thereto at -4.degree. C., thereby being allowed to react for
24 hours. Thereafter, 0.05 g of methanol was added at room
temperature to this reaction mixture liquid, and then the liquid
was stirred to obtain a homogeneous solution. The homogeneous
solution thus obtained was gradually added to 100 g of methanol to
obtain 9.7 g of a white precipitate. This white precipitate was
dried under reduced pressure to obtain a polymer (I). The
weight-average molecular weight of this polymer was 50000.
[0223] Placed in a 100-mL flask were 19.8 g of styrene, 0.2 g of
methacrylic acid and 0.1 g of benzoyl peroxide, and the mixture was
stirred to dissolve. Then, the mixture was sealed and allowed to
react at 70.degree. C. for 12 hours with reflux. A polymer thus
obtained was granulated and then washed with methanol.
Subsequently, the polymer was dried at 50.degree. C. for about 8
hours to obtain a polymer (J). The weight-average molecular weight
of the polymer obtained was 250000.
[0224] Dissolved in 20 g of toluene were 6.0 g of the polymer (I),
4.0 g of the polymer (J), 0.01 g of diphenylsilicone (produced by
Shin-Etsu Chemical Co., Ltd.) having a viscosity of 500 CS and 0.05
g of n-octadecyl-3-(4-hydroxy-3,5-t-dibutylphenyl)propionate, and
the mixture was added to about 300 g of methanol to precipitate a
solid. This solid was dried at 40.degree. C. for 6 hours to obtain
a desired resin composition. This resin composition was hot-pressed
to produce a molding material having a thickness of 2 mm. This
molding material was used as a sample fragment. The above-mentioned
evaluations were carried out using this sample fragment. The
evaluation results are shown in Table 5.
5 TABLE 5 Example 8 Example 9 item unit Polymer I Polymer J Polymer
I Polymer J Molecular weight g/mol 97000 250000 50000 250000 (MW)
Mixing ratio % by weight 60 40 60 40 Heterocycle mol % 0.55 0 0.55
0 amount Carboxyl group mol % 0 0.53 0 1.06 amount
Heterocycle/carboxyl mol/mol 1.04 0.52 group ratio Antioxidant E %
by weight 0.5 0.5 Silicone amount D % by weight 0.1 0.1 Fluidity
(MI) g/10 minutes 15 12 Water absorption % 0.10 0.11 Heat
resistance .degree. C. 147 142 (Tg) Relative -- 2.3 2.3
permittivity Bending strength Mpa 80 82 Transparency % 85 86
Birefringence -- 1 .times. 10.sup.-6 1 .times. 10.sup.-6 Change in
hue -- 0.12 0.11
COMPARATIVE EXAMPLE 4
[0225] An experiment was carried out in the same manner as in
Example 7 except using only 10.0 g of indene and not using
vinylpyridine and methylene chloride in the synthesis of the
polymer (I), and using only 20.0 g of styrene and not using
methacrylic acid in the synthesis of the polymer (H). The
above-mentioned evaluations were conducted using this sample
fragment. The evaluation results are shown in Table 6.
COMPARATIVE EXAMPLE 5
[0226] An experiment was carried out in the same manner as in
Example 7 except not using 0.01 g of diphenylsilicone having a
viscosity of 500 CS (produced by Shin-Etsu Chemical Co., Ltd.) and
0.05 g of n-octadecyl-3-(4-hydroxy-3,5-t-dibutylphenyl)propionate.
The above-mentioned evaluations were conducted using this sample
fragment. The evaluation results are shown in Table 6.
6 TABLE 6 Comparative Example 4 Comparative Example 5 item unit
Polymer I Polymer J Polymer I Polymer J Molecular weight g/mol
15000 250000 15000 250000 (Mw) Mixing ratio % by weight 60 40 60 40
Heterocycle mol % 0 0 0.55 0 amount Carboxyl group mol % 0 0 0 0.53
amount Heterocycle/carboxyl mol/mol -- 1.04 group ratio Antioxidant
E % by weight 0.5 0 Silicone amount D % by weight 0.1 0 Fluidity
(MI) %/ 14 15 10 minutes Water absorption % 0.09 0.09 Heat
resistance .degree. C. 142 143 (Tg) Relative -- 2.2 2.2
permittivity Bending strength MPa 80 80 Transparency % 42 85
Birefringence -- 1 .times. 10.sup.-6 1 .times. 10.sup.-6 Change in
hue -- 0.15 3.7
INDUSTRIAL APPLICABILITY
[0227] The present invention can provide resin compositions having
low hygroscopicity, low birefringence and low permittivity, being
excellent in fluidity, causing little change in color upon heating,
and excelling in mold release characteristics in injection molding.
Furthermore, the use of a molding material, a sheet or a film
obtained by molding these resin compositions can provide an optical
part having low hygroscopicity, low birefringence and low
permittivity.
* * * * *