U.S. patent application number 15/698786 was filed with the patent office on 2018-06-28 for polymer, resin composition and resin molded product.
This patent application is currently assigned to JSR CORPORATION. The applicant listed for this patent is JSR CORPORATION. Invention is credited to Toshiaki Kadota, Yuki Kitamura, Nobuyuki Miyaki, Yuuya Nawate, Ryoji Tatara, Teruhiko Umehara.
Application Number | 20180179335 15/698786 |
Document ID | / |
Family ID | 56879529 |
Filed Date | 2018-06-28 |
United States Patent
Application |
20180179335 |
Kind Code |
A9 |
Nawate; Yuuya ; et
al. |
June 28, 2018 |
POLYMER, RESIN COMPOSITION AND RESIN MOLDED PRODUCT
Abstract
A polymer includes a first structural unit represented by
formula (1-1), (1-2) or (1-3) and a second structural unit
represented by formula (2) or (3). In the formulae (1-1) to (1-3),
(2) and (3), R.sup.1, R.sup.10 and R.sup.11 each represent a
halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon
atoms, a monovalent halogenated hydrocarbon group having 1 to 20
carbon atoms, a nitro group or a cyano group; Zs each represent
--O-- or --S--; R.sup.4s each represent a methylene group or an
alkylene group having 2 to 4 carbon atoms; and L represents a
divalent group represented by formula (2-1). In the formula (2-1),
R.sup.a represents a divalent alicyclic hydrocarbon group having 5
to 30 ring atoms or a divalent fluorinated alicyclic hydrocarbon
group having 5 to 30 ring atoms. ##STR00001##
Inventors: |
Nawate; Yuuya; (Tokyo,
JP) ; Kitamura; Yuki; (Tokyo, JP) ; Tatara;
Ryoji; (Tokyo, JP) ; Umehara; Teruhiko;
(Tokyo, JP) ; Miyaki; Nobuyuki; (Tokyo, JP)
; Kadota; Toshiaki; (Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JSR CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
JSR CORPORATION
Tokyo
JP
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20170369649 A1 |
December 28, 2017 |
|
|
Family ID: |
56879529 |
Appl. No.: |
15/698786 |
Filed: |
September 8, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2016/053721 |
Feb 8, 2016 |
|
|
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15698786 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 71/00 20130101;
C08L 73/00 20130101; C08G 65/40 20130101; C08L 71/10 20130101 |
International
Class: |
C08G 65/40 20060101
C08G065/40 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 11, 2015 |
JP |
2015-048511 |
Oct 21, 2015 |
JP |
2015-207564 |
Claims
1. A polymer comprising: a first structural unit represented by
formula (1-1), (1-2) or (1-3); and a second structural unit
represented by formula (2) or (3), ##STR00027## wherein in the
formulae (1-1) to (1-3), R.sup.1 each independently represents a
halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon
atoms, a monovalent halogenated hydrocarbon group having 1 to 20
carbon atoms, a nitro group or a cyano group; and n is each
independently an integer of 0 to 2, wherein, in a case where n is
2, a plurality of R.sup.1s are identical or different, wherein the
plurality of R.sup.1s optionally taken together represent a ring
structure through binding, ##STR00028## wherein in the formula (2),
R.sup.10 and R.sup.11 each independently represent a halogen atom,
a monovalent hydrocarbon group having 1 to 20 carbon atoms, a
monovalent halogenated hydrocarbon group having 1 to 20 carbon
atoms, a nitro group or a cyano group; e and f are each
independently an integer of 0 to 2; a and b are each independently
an integer of 0 to 8, wherein, in a case where a is no less than 2,
a plurality of R.sup.10s are identical or different, wherein the
plurality of R.sup.10s optionally taken together represent a ring
structure through binding, and in a case where b is no less than 2,
a plurality of R.sup.11s are identical or different, wherein the
plurality of R.sup.11s optionally taken together represent a ring
structure through binding; Zs each independently represent --O-- or
--S--; R.sup.4s each independently represent a methylene group or
an alkylene group having 2 to 4 carbon atoms; v is an integer of 0
to 2, wherein, in a case where v is 2, two R.sup.4s are identical
or different, and two Zs are identical or different; w is an
integer of 0 to 2, wherein, in a case where w is 2, two R.sup.4s
are identical or different, and two Zs are identical or different;
L represents a divalent group represented by formula (2-1); and y
is an integer of 1 to 3, wherein, in a case where y is no less than
2, a plurality of Ls are identical or different, and in a case
where y is no less than 2 and a is no less than 1, a plurality of
R.sup.10s are identical or different, ##STR00029## wherein in the
formula (2-1), R.sup.a represents a divalent alicyclic hydrocarbon
group having 5 to 30 ring atoms or a divalent fluorinated alicyclic
hydrocarbon group having 5 to 30 ring atoms, and ##STR00030##
wherein in the formula (3), R.sup.20 represents a monovalent
hydrocarbon group having 1 to 20 carbon atoms or a monovalent
halogenated hydrocarbon group having 1 to 20 carbon atoms; g is an
integer of 1 to 4, wherein, in a case where g is no less than 2, a
plurality of R.sup.20s are identical or different, wherein the
plurality of R.sup.20s optionally taken together represent a ring
structure through binding; Ys each independently represent --O-- or
--S--; R.sup.5s each independently represent a methylene group or
an alkylene group having 2 to 4 carbon atoms; t is an integer of 0
to 2, wherein, in a case where t is 2, two R.sup.5s are identical
or different, and two Ys are identical or different; and u is an
integer of 0 to 2, wherein, in a case where u is 2, two R.sup.5s
are identical or different, and two Ys are identical or
different.
2. The polymer according to claim 1, wherein in the formula (2-1),
R.sup.a represents a monocyclic alicyclic hydrocarbon group having
5 to 15 ring atoms or a monocyclic fluorinated alicyclic
hydrocarbon group having 5 to 15 ring atoms.
3. The polymer according to claim 2, wherein in the formula (2-1),
R.sup.a represents a monocyclic alicyclic hydrocarbon group having
5 to 10 ring atoms or a monocyclic fluorinated alicyclic
hydrocarbon group having 5 to 10 ring atoms.
4. The polymer according to claim 1, wherein in the formula (2-1),
R.sup.a represents a polycyclic alicyclic hydrocarbon group having
7 to 30 ring atoms or a polycyclic fluorinated alicyclic
hydrocarbon group having 7 to 30 ring atoms.
5. The polymer according to claim 1, wherein the polymer has a
polystyrene equivalent weight average molecular weight of no less
than 500 and no greater than 300,000.
6. A resin composition comprising the polymer according to claim 1
and an organic solvent.
7. A resin molded product comprising the polymer according claim 1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation application of
International Application No. PCT/JP2016/053721, filed Feb. 8,
2016, which claims priority to Japanese Patent Application No.
2015-048511, filed Mar. 11, 2015 and to Japanese Patent Application
No. 2015-207564, filed Oct. 21, 2015. The contents of these
applications are incorporated herein by reference in their
entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The present invention relates to a polymer, a resin
composition and a resin molded product.
Discussion of the Background
[0003] A polymer obtained by copolymerizing a dihydric phenol
monomer and an aromatic dicarboxylic acid monomer has high heat
resistance and is highly transparent, thus being widely used in the
fields related to electricity, automobiles, machineries, and the
like. In these fields, the polymer is generally dissolved in a
solvent to prepare a resin composition, and then a resin molded
product such as a film is formed from the resin composition to find
various uses.
[0004] For example, Japanese Unexamined Patent Application,
Publication No. H8-269214 discloses a film formed from a resin
composition prepared by dissolving, in methylene chloride, a
polyarylate obtained by copolymerizing bisphenol A, which is a
dihydric phenol monomer, with terephthalic acid and isophthalic
acid, which are aromatic dicarboxylic acid monomers.
[0005] In recent years, meanwhile, the use of halogen organic
solvents such as methylene chloride have been avoided because of
concerns about adverse effects on the environment and human health,
and thus replacing them with halogen-free organic solvents have
been desired.
[0006] In a case where the resin molded product is to be used at
high temperatures, the polymer needs to be resistant to heat so as
to inhibit the heat deterioration of the resin molded product.
[0007] As a polymer with increased solubility in a halogen-free
organic solvent, a polymer having an improved structure of the
dihydric phenol monomer has been studied. For example, Japanese
Unexamined Patent Application, Publication No. 2003-313491 suggests
that a polyarylate prepared by using, as a dihydric phenol monomer,
a sulfur atom-containing monomer such as bis(4-hydroxyphenyl)
sulfone has increased solubility in a halogen-free organic
solvent.
SUMMARY OF THE INVENTION
[0008] According to one aspect of the present invention, a polymer
includes a first structural unit represented by formula (1-1),
(1-2) or (1-3), and a second structural unit represented by formula
(2) or (3).
##STR00002##
In the formulae (1-1) to (1-3), R.sup.1 each independently
represents a halogen atom, a monovalent hydrocarbon group having 1
to 20 carbon atoms, a monovalent halogenated hydrocarbon group
having 1 to 20 carbon atoms, a nitro group or a cyano group; and n
is each independently an integer of 0 to 2, wherein, in a case
where n is 2, a plurality of R.sup.1s are identical or different,
wherein the plurality of R.sup.1s optionally taken together
represent a ring structure through binding.
##STR00003##
In the formula (2), R.sup.10 and R.sup.11 each independently
represent a halogen atom, a monovalent hydrocarbon group having 1
to 20 carbon atoms, a monovalent halogenated hydrocarbon group
having 1 to 20 carbon atoms, a nitro group or a cyano group; e and
f are each independently an integer of 0 to 2; a and b are each
independently an integer of 0 to 8, wherein, in a case where a is
no less than 2, a plurality of R.sup.10s are identical or
different, wherein the plurality of R.sup.10s optionally taken
together represent a ring structure through binding, and in a case
where b is no less than 2, a plurality of R.sup.11s are identical
or different, wherein the plurality of R.sup.11s optionally taken
together represent a ring structure through binding; Zs each
independently represent --O-- or --S--; R.sup.4s each independently
represent a methylene group or an alkylene group having 2 to 4
carbon atoms; v is an integer of 0 to 2, wherein, in a case where v
is 2, two R.sup.4s are identical or different, and two Zs are
identical or different; w is an integer of 0 to 2, wherein, in a
case where w is 2, two R.sup.4s are identical or different, and two
Zs are identical or different; L represents a divalent group
represented by formula (2-1); and y is an integer of 1 to 3,
wherein, in a case where y is no less than 2, a plurality of Ls are
identical or different, and in a case where y is no less than 2 and
a is no less than 1, a plurality of R.sup.10s are identical or
different.
##STR00004##
In the formula (2-1), R.sup.a represents a divalent alicyclic
hydrocarbon group having 5 to 30 ring atoms or a divalent
fluorinated alicyclic hydrocarbon group having 5 to 30 ring atoms,
and
##STR00005##
In the formula (3), R.sup.20 represents a monovalent hydrocarbon
group having 1 to 20 carbon atoms or a monovalent halogenated
hydrocarbon group having 1 to 20 carbon atoms; g is an integer of 1
to 4, wherein, in a case where g is no less than 2, a plurality of
R.sup.20s are identical or different, wherein the plurality of
R.sup.20s optionally taken together represent a ring structure
through binding; Ys each independently represent --O-- or --S--;
R.sup.5s each independently represent a methylene group or an
alkylene group having 2 to 4 carbon atoms; t is an integer of 0 to
2, wherein, in a case where t is 2, two R.sup.5s are identical or
different, and two Ys are identical or different; and u is an
integer of 0 to 2, wherein, in a case where u is 2, two R.sup.5s
are identical or different, and two Ys are identical or
different.
[0009] According to another aspect of the present invention, a
resin composition includes the polymer and an organic solvent.
[0010] According to further aspect of the present invention, a
resin molded product includes the polymer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIGURE shows a .sup.1H-NMR spectrum of a polymer of Example
1.
DESCRIPTION OF EMBODIMENTS
[0012] According to an embodiment of the invention made for solving
the aforementioned problems, a polymer has a first structural unit
represented by the following formula (1-1), (1-2) or (1-3) and a
second structural unit represented by the following formula (2) or
(3).
##STR00006##
[0013] In the formulae (1-1) to (1-3), R.sup.1 each independently
represents a halogen atom, a monovalent hydrocarbon group having 1
to 20 carbon atoms, a monovalent halogenated hydrocarbon group
having 1 to 20 carbon atoms, a nitro group or a cyano group; and n
is each independently an integer of 0 to 2, wherein, in a case
where n is 2, a plurality of R.sup.1s may be identical or
different, wherein the plurality of R.sup.1s optionally taken
together may represent the ring structure through binding.
##STR00007##
[0014] In the formula (2), R.sup.10 and R.sup.11 each independently
represent a halogen atom, a monovalent hydrocarbon group having 1
to 20 carbon atoms, a monovalent halogenated hydrocarbon group
having 1 to 20 carbon atoms, a nitro group or a cyano group; e and
f are each independently an integer of 0 to 2; a and b are each
independently an integer of 0 to 8, wherein, in a case where a is
no less than 2, a plurality of R.sup.10s may be identical or
different, wherein the plurality of R.sup.10s optionally taken
together may represent the ring structure through binding, and in a
case where b is no less than 2, a plurality of R.sup.11s may be
identical or different, wherein the plurality of R.sup.11s
optionally taken together may represent the ring structure through
binding; Zs each independently represent --O-- or --S--; R.sup.4s
each independently represent a methylene group or an alkylene group
having 2 to 4 carbon atoms; v is an integer of 0 to 2, wherein, in
a case where v is 2, two R.sup.4s may be identical or different,
and two Zs may be identical or different; w is an integer of 0 to
2, wherein, in a case where w is 2, two R.sup.4s may be identical
or different, and two Zs may be identical or different; L
represents a divalent group represented by the following formula
(2-1); and y is an integer of 1 to 3, wherein, in a case where y is
no less than 2, a plurality of Ls may be identical or different,
and in a case where y is no less than 2 and a is no less than 1, a
plurality of R.sup.10s may be identical or different.
##STR00008##
[0015] In the formula (2-1), R.sup.a represents a divalent
alicyclic hydrocarbon group having 5 to 30 ring atoms or a divalent
fluorinated alicyclic hydrocarbon group having 5 to 30 ring
atoms.
##STR00009##
[0016] In the formula (3), R.sup.20 represents a monovalent
hydrocarbon group having 1 to 20 carbon atoms or a monovalent
halogenated hydrocarbon group having 1 to 20 carbon atoms; g is an
integer of 1 to 4, wherein, in a case where g is no less than 2, a
plurality of R.sup.20s may be identical or different, wherein the
plurality of R.sup.20s optionally taken together may represent the
ring structure through binding; Ys each independently represent
--O-- or --S--; R.sup.5s each independently represent a methylene
group or an alkylene group having 2 to 4 carbon atoms; t is an
integer of 0 to 2, wherein, in a case where t is 2, two R.sup.5s
may be identical or different, and two Ys may be identical or
different; and u is an integer of 0 to 2, wherein, in a case where
u is 2, two R.sup.5s may be identical or different, and two Ys may
be identical or different.
[0017] Further embodiments of the present invention involve a resin
composition containing the polymer and an organic solvent, and a
resin molded product containing the polymer.
[0018] As referred to herein, the "hydrocarbon group" may involve a
chain hydrocarbon group and a cyclic hydrocarbon group. The
"hydrocarbon group" may be either a saturated hydrocarbon group or
an unsaturated hydrocarbon group. The "chain hydrocarbon group" as
referred to means a hydrocarbon group not including a ring
structure but constructed with only a chain structure. The "chain
hydrocarbon group" may involve both a straight chain hydrocarbon
group and a branched hydrocarbon group. The "cyclic hydrocarbon
group" as referred to means a hydrocarbon group constructed with a
ring structure and may involve both an alicyclic hydrocarbon group
and an aromatic hydrocarbon group. The "alicyclic hydrocarbon
group" as referred to means a hydrocarbon group which includes not
an aromatic ring structure but only an alicyclic structure as the
ring structure, and may involve both a monocyclic alicyclic
hydrocarbon group and a polycyclic alicyclic hydrocarbon group.
However, it is not necessary to be constructed with only an
alicyclic structure, and a chain structure may be included as a
part thereof. The "aromatic hydrocarbon group" as referred to means
a hydrocarbon group which includes an aromatic ring structure as
the ring structure, and may involve both a monocyclic aromatic
hydrocarbon group and a polycyclic aromatic hydrocarbon group.
However, it is not necessary to be constructed with only an
aromatic ring structure, and a chain structure and/or an alicyclic
structure may be included as a part thereof. The term "number of
ring atoms" as referred to means the number of atoms constituting a
ring structure. In a case where the ring structure is polycyclic,
it means the number of atoms constituting the polycyclic
structure.
[0019] The embodiment of the present invention is capable of
providing a polymer having superior heat resistance and increased
solubility in various types of organic solvents, and a resin
composition and a resin molded product containing the polymer.
[0020] The following will describe in detail, a polymer, a resin
composition and a resin molded product according to the embodiment
of the present invention.
Polymer
[0021] The polymer according to an embodiment of the present
invention (hereinafter, may be also referred to as "(A) polymer" or
"polymer (A)") has the first structural unit and the second
structural unit. The polymer (A) may have two or more types of each
of the above structural units. It is to be noted that, as long as
the polymer (A) has the first and second structural units, the
arrangement of each structural unit and other structures of the
polymer (A) are not particularly limited. For example, the polymer
(A) may have any structural unit(s) other than the first and second
structural units. In addition, the polymer (A) may have repeating
units (a) to (f) that include the first and second structural units
as will be described below, and may further have other repeating
unit(s).
[0022] The polymer (A) has, by virtue of the first and second
structural units, superior heat resistance and increased solubility
in various types of organic solvents. Although not necessarily
clarified, and without wishing to be bound by any theory, the
reason for achieving the effects described above due to the polymer
(A) having the aforementioned constitutions is mainly inferred as
in the following (1) and (2).
[0023] (1) The incorporation of the first structural unit which has
a specific heterocyclic structure including two nitrogen atoms
enables an appropriate adjustment of polarization of polymer
chains, while the incorporation of the second structural unit which
has a structure in which aromatic rings bind to each other through
a relatively bulky ring structure or a structure including a
benzene ring with substituents bonded thereto enables inhibition of
aggregation of polymer chains. Consequently, an increase in the
solubility in various types of organic solvents is enabled.
[0024] (2) The incorporation of the second structural unit which
has a structure in which aromatic rings bind to each other through
a relatively bulky ring structure or a structure including a
benzene ring with substituents bonded thereto enables an
appropriate adjustment of the rigidity of polymer chains. The
polymer (A) accordingly has superior heat resistance.
[0025] The following will describe the first and second structural
units and other structural units which may be optionally contained
in the polymer (A).
First Structural Unit
[0026] The first structural unit is represented by the following
formula (1-1), (1-2) or (1-3).
##STR00010##
[0027] In the above formulae (1-1) to (1-3), R.sup.1 each
independently represents a halogen atom, a monovalent hydrocarbon
group having 1 to 20 carbon atoms, a monovalent halogenated
hydrocarbon group having 1 to 20 carbon atoms, a nitro group or a
cyano group; and n is each independently an integer of 0 to 2,
wherein, in a case where n is 2, a plurality of R.sup.1s may be
identical or different, wherein the plurality of R.sup.1s
optionally taken together may represent the ring structure through
binding.
[0028] The halogen atom which may be represented by R.sup.1 is
exemplified by a fluorine atom, a chlorine atom, a bromine atom, an
iodine atom, and the like.
[0029] The monovalent hydrocarbon group having 1 to 20 carbon atoms
which may be represented by R.sup.1 is exemplified by a monovalent
chain hydrocarbon group, a monovalent alicyclic hydrocarbon group,
a monovalent aromatic hydrocarbon group, and the like.
[0030] Examples of the monovalent chain hydrocarbon group
include:
[0031] alkyl groups such as a methyl group, an ethyl group, an
n-propyl group, an i-propyl group, an n-butyl group, an i-butyl
group, a sec-butyl group, a t-butyl group and an n-pentyl
group;
[0032] alkenyl groups such as an ethenyl group, a propenyl group, a
butenyl group and a pentenyl group;
[0033] alkynyl groups such as an ethynyl group, a propynyl group, a
butynyl group and a pentenyl group; and the like.
[0034] Examples of the monovalent alicyclic hydrocarbon group
include:
[0035] monocyclic cycloalkyl groups such as a cyclopropyl group, a
cyclobutyl group, a cyclopentyl group and a cyclohexenyl group;
[0036] polycyclic cycloalkyl groups such as a norbornyl group and
an adamantyl group;
[0037] monocyclic cycloalkenyl groups such as a cyclopropenyl
group, a cyclobutenyl group, a cyclopentenyl group and a cyclohexyl
group;
[0038] polycyclic cycloalkenyl groups such as a norbornenyl group;
and the like.
[0039] Examples of the monovalent aromatic hydrocarbon group
include:
[0040] aryl groups such as a phenyl group, a tolyl group, a xylyl
group, a naphthyl group and an anthryl group;
[0041] aralkyl groups such as a benzyl group, a phenethyl group, a
phenylpropyl group and a naphthylmethyl group; and the like.
[0042] The monovalent halogenated hydrocarbon group having 1 to 20
carbon atoms which may be represented by R.sup.1 is exemplified by
a group obtained by substituting a part or all of hydrogen atoms
included in the monovalent hydrocarbon group having 1 to 20 carbon
atoms which is exemplified as the group represented by R.sup.1 with
halogen atoms such as a fluorine atom, a chlorine atom, a bromine
atom, an iodine atom, and the like.
[0043] R.sup.1 represents, in light of an improvement of the
polymerization reactivity of the monomer for providing the first
structural unit, preferably a halogen atom, a monovalent
hydrocarbon group having 1 to 3 carbon atoms, a monovalent
halogenated hydrocarbon group having 1 to 3 carbon atoms, a nitro
group or a cyano group, and more preferably a fluorine atom, a
chlorine atom, a methyl group, a nitro group or a cyano group. From
the same perspective, n is preferably 0 or 1, and more preferably
0.
[0044] In light of the improvement of the polymerization reactivity
of the monomer for providing the first structural unit, a position
of one atomic bonding with respect to another atomic bonding in the
first structural unit is preferably the meta position or the para
position, and more preferably the meta position.
[0045] In addition, the first structural unit is preferably a
structural unit which is represented by the above formula (1-2)
having a pyrimidine skeleton, in light of the improvement of the
polymerization reactivity of the monomer for providing the first
structural unit and the improvement of the solubility in various
types of organic solvents.
[0046] The lower limit of the proportion of the first structural
unit contained in the polymer (A) with respect to the total
structural units contained in the polymer (A) is preferably 5 mol
%, more preferably 10 mol %, still more preferably 20 mol %, and
particularly preferably 30 mol %. The upper limit of the proportion
is preferably 67 mol %, more preferably 60 mol %, still more
preferably 55 mol %, and particularly preferably 50 mol %. When the
proportion falls within the above range, a further improvement of
the solubility in various types of organic solvents is enabled.
Second Structural Unit
[0047] The second structural unit is represented by the following
formula (2) or (3).
##STR00011##
[0048] In the above formula (2), R.sup.10 and R.sup.11 each
independently represent a halogen atom, a monovalent hydrocarbon
group having 1 to 20 carbon atoms, a monovalent halogenated
hydrocarbon group having 1 to 20 carbon atoms, a nitro group or a
cyano group; e and f are each independently an integer of 0 to 2; a
and b are each independently an integer of 0 to 8, wherein, in a
case where a is no less than 2, a plurality of R.sup.10s may be
identical or different, wherein the plurality of R.sup.10s
optionally taken together may represent the ring structure through
binding, and in a case where b is no less than 2, a plurality of
R.sup.11s may be identical or different, wherein the plurality of
R.sup.11s optionally taken together may represent the ring
structure through binding; Zs each independently represent --O-- or
--S--; R.sup.4s each independently represent a methylene group or
an alkylene group having 2 to 4 carbon atoms; v is an integer of 0
to 2, wherein, in a case where v is 2, two R.sup.4s may be
identical or different, and two Zs may be identical or different; w
is an integer of 0 to 2, wherein, in a case where w is 2, two
R.sup.4s may be identical or different, and two Zs may be identical
or different; L represents a divalent group represented by the
following formula (2-1); and y is an integer of 1 to 3, wherein, in
a case where y is no less than 2, a plurality of Ls may be
identical or different, and in a case where y is no less than 2 and
a is no less than 1, a plurality of R.sup.10s may be identical or
different.
##STR00012##
[0049] In the above formula (2-1), R.sup.a represents a divalent
alicyclic hydrocarbon group having 5 to 30 ring atoms or a divalent
fluorinated alicyclic hydrocarbon group having 5 to 30 ring
atoms.
##STR00013##
[0050] In the above formula (3), R.sup.20 represents a monovalent
hydrocarbon group having 1 to 20 carbon atoms or a monovalent
halogenated hydrocarbon group having 1 to 20 carbon atoms; g is an
integer of 1 to 4, wherein, in a case where g is no less than 2, a
plurality of R.sup.20s may be identical or different, wherein the
plurality of R.sup.20s optionally taken together may represent the
ring structure through binding; Ys each independently represent
--O-- or --S--; R.sup.5s each independently represent a methylene
group or an alkylene group having 2 to 4 carbon atoms; t is an
integer of 0 to 2, wherein, in a case where t is 2, two R.sup.5s
may be identical or different, and two Ys may be identical or
different; and u is an integer of 0 to 2, wherein, in a case where
u is 2, two R.sup.5s may be identical or different, and two Ys may
be identical or different.
[0051] The halogen atoms which may be represented by R.sup.10 and
R.sup.11 are exemplified by halogen atoms similar to those
exemplified as the halogen atom which may be represented by
R.sup.1.
[0052] The monovalent hydrocarbon groups each having 1 to 20 carbon
atoms which may be represented by R.sup.10, R.sup.11 and R.sup.20
are exemplified by a monovalent hydrocarbon group having 1 to 20
carbon atoms which is exemplified as the group represented by
R.sup.1.
[0053] The monovalent halogenated hydrocarbon groups each having 1
to 20 carbon atoms which may be represented by R.sup.10, R.sup.11
and R.sup.20 are exemplified by groups obtained by substituting a
part or all of hydrogen atoms included in the monovalent
hydrocarbon group having 1 to 20 carbon atoms which is exemplified
as the group represented by R.sup.1 with halogen atoms such as a
fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and
the like.
[0054] In light of the improvement of the polymerization reactivity
of the monomer for providing the second structural unit, R.sup.10
and R.sup.11 each represent: preferably a halogen atom, a
monovalent hydrocarbon group having 1 to 6 carbon atoms, a
monovalent halogenated hydrocarbon group having 1 to 6 carbon
atoms, a nitro group and a cyano group; more preferably a fluorine
atom, a chlorine atom, a methyl group, a t-butyl group, a phenyl
group, a nitro group and a cyano group; still more preferably a
fluorine atom, a methyl group, a t-butyl group and a phenyl group;
and particularly preferably a methyl group.
[0055] In light of the improvement of the polymerization reactivity
of the monomer for providing the second structural unit and the
bulkiness, R.sup.20 represents: preferably a monovalent hydrocarbon
group having 3 to 20 carbon atoms and a monovalent halogenated
hydrocarbon having 3 to 20 carbon atoms; more preferably an alkyl
group having 3 to 10 carbon atoms and an aryl group having 6 to 10
carbon atoms; still more preferably a t-alkyl group, a phenyl group
and a naphthyl group; and particularly preferably a t-butyl
group.
[0056] In light of the improvement of the polymerization reactivity
of the monomer for providing the second structural unit, a and b
are each preferably 0 to 2, more preferably 0 and 1, and still more
preferably 0. From the same perspective, e and f are each
preferably 0 and 1, and more preferably 0. In light of the
improvement of the polymerization reactivity of the monomer for
providing the second structural unit and the bulkiness, g is
preferably 1 to 3, and more preferably 1 or 2.
[0057] Z and Y each preferably represent --O-- in light of the
structural stability of the polymer (A).
[0058] The alkylene groups each having 2 to 4 carbon atoms which
may be represented by R.sup.4 and R.sup.5 are exemplified by an
ethylene group, an n-propylene group, an isopropylene group, an
n-butylene group, a sec-butylene group and t-butylene group.
[0059] R.sup.4 and R.sup.5 each represent, in light of the
improvement of the polymerization reactivity of the monomer for
providing the second structural unit, preferably a methylene group
and an ethylene group.
[0060] In light of the improvement of the polymerization reactivity
of the monomer for providing the second structural unit, v and w
are each preferably 0 and 1, and more preferably 0. From the same
perspective, t and u are each preferably 0 and 1, and more
preferably 0.
[0061] The divalent alicyclic hydrocarbon group having 5 to 30 ring
atoms which may be represented by R.sup.a is exemplified by a
monocyclic alicyclic hydrocarbon group having 5 to 15 ring atoms, a
monocyclic fluorinated alicyclic hydrocarbon group having 5 to 15
ring atoms, a polycyclic alicyclic hydrocarbon group having 7 to 30
ring atoms, and a polycyclic fluorinated alicyclic hydrocarbon
group having 7 to 30 ring atoms.
[0062] Examples of the monocyclic alicyclic hydrocarbon group
having 5 to 15 ring atoms include a cyclopentane-1,1-diyl group, a
cyclohexane-1,1-diyl group, a cyclopentane-3,3-diyl group, a
cyclohexane-3,3-diyl group, a cyclooctane-1,1-diyl group, a
cyclodecane-1,1-diyl group, a cyclododecane-1,1-diyl group, a group
obtained by substituting a part or all of hydrogen atoms included
in the above groups with monovalent chain hydrocarbon groups each
having 1 to 20 carbon atoms, and the like.
[0063] The monocyclic alicyclic hydrocarbon group having 5 to 15
ring atoms is preferably an alicyclic hydrocarbon group having 5 to
10 ring atoms, in light of further improving the solubility in
various types of organic solvents while maintaining high heat
resistance.
[0064] Examples of the monocyclic fluorinated alicyclic hydrocarbon
group having 5 to 15 ring atoms include groups obtained by
substituting with fluorine atoms a part or all of hydrogen atoms
included in the group exemplified as the monocyclic alicyclic
hydrocarbon group having 5 to 15 ring atoms, and the like.
[0065] The monocyclic fluorinated alicyclic hydrocarbon group
having 5 to 15 ring atoms is preferably a fluorinated alicyclic
hydrocarbon group having 5 to 10 ring atoms in light of further
improving the solubility in various types of organic solvents while
maintaining high heat resistance.
[0066] Examples of the polycyclic alicyclic hydrocarbon group
having 7 to 30 ring atoms include: groups obtained by removing two
hydrogen atoms bonded to one carbon atom included in the polycyclic
alicyclic hydrocarbon group such as norbornane, norbornene,
adamantane, tricyclo[5.2.1.0.sup.2,6]decane,
tricyclo[5.2.1.0.sup.2,6]heptane, pinane, camphane, decalin,
nortricyclene, perhydroanthracene, perhydroazulene,
cyclopentanohydrophenanthrene, bicyclo[2.2.2]-2-octene, and the
like; groups obtained by substituting a part or all of hydrogen
atoms included in the above groups with monovalent chain
hydrocarbon groups each having 1 to 20 carbon atoms; and the
like.
[0067] Examples of the polycyclic fluorinated alicyclic hydrocarbon
group having 7 to 30 ring atoms include a group obtained by
substituting with fluorine atoms a part or all of hydrogen atoms
included in the group exemplified as the polycyclic alicyclic
hydrocarbon group having 7 to 30 ring atoms, and the like.
[0068] In light of further improving solubility in various types of
organic solvents while maintaining high heat resistance, the
divalent group represented by the above formula (2-1) is preferably
a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, and a
group obtained by substituting a part or all of hydrogen atoms
included in the above groups with monovalent chain hydrocarbon
groups each having 1 to 3 carbon atoms, more preferably a group
obtained by substituting a part or all of hydrogen atoms included
in a cyclohexane-1,1-diyl group and a cyclohexane-1,1-diyl group
with monovalent chain hydrocarbon groups each having 1 to 3 carbon
atoms, still more preferably a group obtained by substituting with
methyl groups a part or all of hydrogen atoms included in a
cyclohexane-1,1-diyl group, and particularly preferably a
3,3,5-trimethylcyclohexane-1,1-diyl group.
[0069] In light of the improvement of the polymerization reactivity
of the monomer for providing the second structural unit, y is
preferably 1 or 2, and more preferably 1.
[0070] In light of the improvement of the polymerization reactivity
of the monomer for providing the second structural unit, a position
of one atomic bonding with respect to another bonding in a benzene
ring of the second structural unit represented by the above formula
(3) is preferably the para position or the meta position, and more
preferably the para position. On the other hand, in light of the
improvement of the solubility of the polymer, the ortho position is
preferred.
[0071] The lower limit of the proportion of the second structural
unit contained in the polymer (A) with respect to the total
structural units contained the polymer (A) is preferably 5 mol %,
more preferably 10 mol %, still more preferably 20 mol %, and
particularly preferably 30 mol %. The upper limit of the proportion
is preferably 67 mol %, more preferably 60 mol %, still more
preferably 55 mol %, and particularly preferably 50 mol %. When the
proportion falls within the above range, a further improvement of
the solubility in various types of organic solvents is enabled
while high heat resistance is maintained.
Other Structural Units
[0072] For the adjustment of molecular weight and the like, the
polymer (A) may have other structural unit(s) different from the
first and second structural units within a range not leading to
impairment of the above effects.
[0073] The other structural units are exemplified by:
[0074] a third structural unit represented by the above formula
(2), wherein L represents a single bond, --O--, --S--, --CO--,
--SO--, --SO.sub.2--, --CONH--, --COO--, a divalent chain
hydrocarbon group having 1 to 20 carbon atoms, a divalent
fluorinated chain hydrocarbon group having 1 to 20 carbon atoms, a
divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or
a divalent fluorinated aromatic hydrocarbon group having 6 to 20
carbon atoms;
[0075] a fourth structural unit represented by the following
formula (4); and the like.
##STR00014##
[0076] In the above formula (4), R.sup.2 represents a halogen atom,
a monovalent hydrocarbon group having 1 to 20 carbon atoms, a
monovalent halogenated hydrocarbon group having 1 to 20 carbon
atoms, a nitro group or a cyano group; i is 1 or 2; h is an integer
of 0 to 8, wherein, in a case where h is no less than 2, a
plurality of R.sup.2s may be identical or different, wherein the
plurality of R.sup.2s optionally taken together may represent the
ring structure through binding; R.sup.3s each independently
represent a methylene group or an alkylene group having 2 to 4
carbon atoms; c is an integer of 0 to 2, wherein, in a case where c
is 2, two R.sup.3s may be identical or different; and d is an
integer of 0 to 2, wherein, in a case where d is 2, two R.sup.as
may be identical or different.
[0077] The halogen atom which may be represented by R.sup.2 is
exemplified by halogen atoms similar to those exemplified as the
halogen atom which may be represented by R.sup.1.
[0078] The monovalent hydrocarbon group having 1 to 20 carbon atoms
which may be represented by R.sup.2 is exemplified by groups
similar to those exemplified as the monovalent hydrocarbon group
having 1 to 20 carbon atoms which may be represented by
R.sup.1.
[0079] The monovalent halogenated hydrocarbon group having 1 to 20
carbon atoms which may be represented by R.sup.2 is exemplified by
a group obtained by substituting a part or all of hydrogen atoms
included in the monovalent hydrocarbon group having 1 to 20 carbon
atoms which is exemplified as the group which may be represented by
R.sup.1, with halogen atoms such as a fluorine atom, a chlorine
atom, a bromine atom, an iodine atom, and the like.
[0080] R.sup.2 represents preferably a monovalent hydrocarbon group
having 1 to 10 carbon atoms, more preferably a monovalent chain
hydrocarbon group having 1 to 10 carbon atoms, still more
preferably a monovalent branched hydrocarbon group having 1 to 10
carbon atoms, and particularly preferably an i-butyl group, a
sec-butyl group or a t-butyl group. When R.sup.2 represents any of
the above-specified groups, a further improvement of the solubility
in various types of organic solvents is enabled.
[0081] The alkylene group having 2 to 4 carbon atoms which may be
represented by R.sup.3 is exemplified by an ethylene group, an
n-propylene group, an isopropylene group, an n-butylene group, a
sec-butylene group and a t-butylene group.
[0082] In light of the improvement of the polymerization reactivity
of the monomer for providing the fourth structural unit, R.sup.3
represents preferably a methylene group or an ethylene group.
[0083] In light of the improvement of the polymerization reactivity
of the monomer for providing the fourth structural unit, c and d
are each preferably 0 or 1, and more preferably 0. From the same
perspective, i is preferably 1.
[0084] In light of the further improvement of the solubility in
various types of organic solvents and the formability, h is
preferably 1 or 2, and more preferably 1.
[0085] Of the other structural units mentioned above, the fourth
structural unit is preferred in light of the further improvement of
the solubility in various types of organic solvents. From the same
perspective, the fourth structural unit is preferably a structural
unit represented by the above formula (4) in which
--O(R.sup.3O).sub.d-- occupies the ortho position with respect to
the --(OR.sup.3).sub.cO--.
[0086] In the case where the polymer (A) has the other structural
unit, the lower limit of the proportion of the other structural
unit contained in the polymer (A) with respect to the total
structural units contained the polymer (A) is preferably 1 mol %,
more preferably 5 mol %, and still more preferably 10 mol %. The
upper limit of the proportion is preferably 40 mol %, and more
preferably 30 mol %. When the proportion falls within the above
range, the adjustment of molecular weight within a range not
leading to impairment of the above effects is enabled.
[0087] In the case where the polymer (A) has the fourth structural
unit, the lower limit of the proportion of the fourth structural
unit contained in the polymer (A) with respect to the total
structural units contained the polymer (A) is preferably 5 mol %,
more preferably 10 mol %, and still more preferably 20 mol %. The
upper limit of the proportion is preferably 40 mol %, and more
preferably 30 mol %. When the proportion falls within the above
range, a further improvement of the solubility in various types of
organic solvents is enabled.
Arrangement of Each Structural Unit
[0088] Although the arrangement of each structural unit in the
polymer (A) is not particularly limited as long as it has the first
and second structural units, it is preferred that the polymer (A)
has the first and second structural units in the main chain in
light of further improving the solubility in various types of
organic solvents while maintaining high heat resistance. The term
"main chain" as referred to herein means in relative terms the
longest linking chain in the polymer.
[0089] When the polymer (A) has the first and second structural
units in the main chain, a decrease in permittivity is facilitated
in the case of employing the polymer (A) for an insulating film for
use in printed wiring boards, and thus, for example, an improvement
of the high frequency wave properties of the printed wiring boards
is enabled.
Repeating Unit
[0090] The polymer (A) having the first and second structural units
in the main chain is exemplified by a polymer having, in the main
chain thereof, a repeating unit (a) represented by the following
formula (a), a repeating unit (b) represented by the following
formula (b), a repeating unit (c) represented by the following
formula (c), a repeating unit (d) represented by the following
formula (d), a repeating unit (e) represented by the following
formula (e), a repeating unit (f) represented by the following
formula (f), any combination of these repeating units (hereinafter,
may be also collectively referred to as "specific repeating
units"), or the like.
##STR00015##
[0091] In the above formulae (a) to (f), R.sup.1 and n are each as
defined in the above formulae (1-1) to (1-3); R.sup.4, R.sup.10,
R.sup.11, a, b, e, f, v, w, y, L and Z are each as defined in the
above formula (2); and R.sup.5, R.sup.20, g, t, u and Y are each as
defined in the above formula (3).
Synthesis Method of Polymer (A)
[0092] The polymer (A) may be obtained by a well-known synthesis
method of poly(thio)ether. The synthesis is achieved through, for
example, a reaction among: a dihalide monomer for providing the
first structural unit; a diol monomer or a dithiol monomer for
providing the second structural unit; and other compound(s), in an
organic solvent under predetermined conditions.
[0093] The other compound(s) may be exemplified by an alkali metal
compound, a chain-end terminator, and a monomer for providing any
of the other structural units mentioned above.
[0094] The alkali metal compound reacts with the diol monomer and
the like to form an alkali metal salt in the processes of the
synthesis of the polymer (A). Examples of the alkali metal compound
include:
[0095] alkali metal hydrides such as lithium hydride, sodium
hydride and potassium hydride;
[0096] alkali metal hydroxides such as lithium hydroxide, sodium
hydroxide and potassium hydroxide;
[0097] alkali metal carbonates such as lithium carbonate, sodium
carbonate and potassium carbonate; and
[0098] alkali metal hydrogencarbonates such as lithium
hydrogencarbonate, sodium hydrogencarbonate and potassium
hydrogencarbonate.
[0099] Of these, alkali metal hydroxides and alkali metal
carbonates are preferred, and sodium hydroxide and potassium
carbonate are more preferred.
[0100] In a case where the alkali metal compound is used, the lower
limit of the amount of the alkali metal compound used is, in terms
of the amount of metal atoms contained in the alkali metal compound
with respect to hydroxyl groups in the total monomers used in the
synthesis of the polymer (A), preferably 1-fold equivalents, more
preferably 1.1-fold equivalents, more preferably 1.2-fold
equivalents, and particularly preferably 1.5-fold equivalents. On
the other hand, the upper limit of the amount of the alkali metal
compound used is preferably 3-fold equivalents, and more preferably
2-fold equivalents.
[0101] The organic solvent is exemplified by N,N-dimethylacetamide,
N,N-dimethylformamide, N-methy-2-pyrrolidone,
1,3-dimethyl-2-imidazolidinone, .gamma.-butyrolactone, sulfolane,
dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl
sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether,
benzophenone, methylene chloride, benzene, toluene, xylene,
dialkoxybenzene (number of carbon atoms in an alkoxy group: 1 to
4), trialkoxybenzene (number of carbon atoms in an alkoxy group: 1
to 4), and the like. These organic solvents may be used either
alone of one type, or in combination of two or more types
thereof.
[0102] In addition to the organic solvents exemplified above, a
solvent that forms an azeotropic mixture with water such as hexane,
cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran,
anisole and phenetole may be further used.
[0103] The lower limit of the reaction temperature in the synthesis
of the polymer (A) is preferably 20.degree. C., and more preferably
100.degree. C. The upper limit of the reaction temperature is
preferably 250.degree. C., and more preferably 180.degree. C. The
lower limit of the reaction time period is preferably 15 min, and
more preferably 1 hr. The upper limit of the reaction time period
is preferably 100 hrs, and more preferably 10 hrs.
Weight Average Molecular Weight (Mw) of Polymer (A)
[0104] The lower limit of the weight average molecular weight (Mw)
of the polymer (A) is preferably 500, more preferably 1,000, still
more preferably 10,000, particularly preferably 20,000, and further
particularly preferably 30,000. The upper limit of the Mw is
preferably 300,000, more preferably 200,000, still more preferably
100,000, and particularly preferably 80,000. When the Mw is no less
than the lower limit, a further improvement of the heat resistance
is enabled. On the other hand, when the Mw is greater than the
upper limit, the formability may be impaired. It is to be noted
that the Mw is determined by gel permeation chromatography (GPC)
under the following conditions.
[0105] Column: "TSKgel .alpha.-M" coupled to "TSKgel Guard Column
.alpha." (each available from Tosoh Corporation), etc.
[0106] Developing solvent: N-methyl-2-pyrrolidone
[0107] Column temperature: 40.degree. C.
[0108] Flow rate: 1.0 mL/min
[0109] Concentration of sample: 0.75% by mass
[0110] Amount of injected sample: 50 .mu.L
[0111] Detector: differential refractometer
[0112] Standard substance: monodisperse polystyrene
Glass Transition Temperature (Tg) of Polymer (A)
[0113] The lower limit of the glass transition temperature of the
polymer (A) is preferably 150.degree. C., more preferably
165.degree. C., still more preferably 180.degree. C., and
particularly preferably 190.degree. C. When the glass transition
temperature is no less than the lower limit, a further improvement
of the heat resistance is enabled. The upper limit of the glass
transition temperature is, for example, 300.degree. C. It is to be
noted that the term "glass transition temperature" as referred to
herein means a value determined by using, for example, a
differential scanning calorimeter in a nitrogen atmosphere at a
rate of temperature rise of 20.degree. C./min.
Resin Composition
[0114] The resin composition contains the polymer (A) and an
organic solvent, and may also contain other components within a
range not leading to impairment of the effects of the present
invention. The resin composition contains the polymer (A) having
superior solubility in the various types of organic solvents, and
may thus be used as a highly versatile resin composition which
finds various uses. Since the resin composition contains the
polymer (A) having superior heat resistance, the heat deterioration
of the resin molded product formed from the resin composition can
be inhibited.
[0115] Examples of the organic solvent include organic solvents
similar to those used in the synthesis of the polymer (A). In
addition, since the resin composition contains the polymer (A)
having superior solubility in various types of organic solvents,
polyhydric alcohol ethers such as diethylene glycol ethyl methyl
ether; polyhydric alcohol partially etherated carboxylates such as
propylene glycol-1-monomethyl ether-2-acetate; carboxylic acid
esters such as methyl 3-methoxypropionate and butyl acetate;
lactones such as .gamma.-butyrolactone; and the like may also be
used as the organic solvent. These organic solvents may be used
either alone of one type, or in combination of two or more types
thereof.
[0116] The lower limit of the content of the polymer (A) in the
resin composition with respect to the total solid content of the
resin composition is preferably 1% by mass, more preferably 10% by
mass, still more preferably 50% by mass, and particularly
preferably 90% by mass. The upper limit of the content is, for
example, 100% by mass.
[0117] The lower limit of the content of the organic solvent in the
resin composition with respect to 100 parts by mass of the polymer
(A) is preferably 50 parts by mass, more preferably 100 parts by
mass, still more preferably 500 parts by mass, particularly
preferably 1,000 parts by mass, further particularly preferably
5,000 parts by mass, and most preferably 10,000 parts by mass. The
upper limit of the content is, for example, 100,000 parts by
mass.
[0118] The other component is exemplified by an antioxidant, a
lubricant, a fire retardant, an antimicrobial, a colorant, a
release agent, a foaming agent, and a polymer other than the
polymer (A). The other component may be used either alone of one
type, or in combination of two or more types thereof.
[0119] Exemplary antioxidant includes a hindered phenol compound, a
phosphorus compound, a sulfur compound, a metal compound, a
hindered amine compound, and the like. Of these, a hindered phenol
compound is preferred.
[0120] It is preferred that the hindered phenol compound has a
molecular weight of no less than 500. Examples of the hindered
phenol compound having a molecular weight of no less than 500
include triethylene
glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
2-4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-3,5-triazine,
pentaerythritol
tetrakis[3-(3,5-t-butyl-4-hydroxyphenyl)propionate],
1,1,3-tris[2-methyl-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-5--
t-butylphenyl]butane,
2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide),
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 3,9-bis[2-[3
-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,dimethylethyl]-2,3-
,8,10-tetraoxaspiro[5.5]undecane, and the like.
[0121] In a case where the resin composition contains an
antioxidant, the lower limit of the content of the antioxidant
contained in the resin composition with respect to 100 parts by
mass of the polymer (A) is preferably 0.01 parts by mass, and more
preferably 0.1 parts by mass. The upper limit of the content is
preferably 10 parts by mass, and more preferably 1 part by
mass.
[0122] The resin composition may be prepared by uniformly mixing
the polymer (A), the organic solvent, and as needed, other
components such as an antioxidant. The resin composition thus
prepared may be in the form of a liquid, a paste, and the like.
Resin Molded Product
[0123] The resin molded product contains the polymer (A), and may
be formed from the resin composition. Due to containing the polymer
(A) having superior heat resistance, the inhibition of the heat
deterioration of the resin molded product is enabled.
[0124] The resin molded product is exemplified by an optical
component, and an insulating film for use in printed wiring
boards.
[0125] Examples of the optical component include:
[0126] optical films such as a retardation sheet and a phase
difference sheet;
[0127] various types of special-purpose lenses such as a conical
lens, a spherical lens, and a cylindrical lens;
[0128] lens arrays; and the like.
[0129] The resin molded product may be produced by, for example, a
metal molding process, an extrusion molding process, a solvent
casting process, or the like. The metal molding process is suited
for the production of lenses. The extrusion molding process and the
solvent casting process are suited, and the extrusion molding is
more preferred, for the production of optical films and insulating
films for use in printed wiring boards.
[0130] The lower limit of the average thickness of the optical film
is preferably 10 .mu.m. The upper limit of the average thickness is
preferably 1,000 .mu.m, and more preferably 500 .mu.m. When the
average thickness is less than the lower limit, sufficient film
strength may not be ensured. On the other hand, when the average
thickness is greater than the upper limit, the transparency of the
film may not be ensured.
[0131] The lower limit of the average thickness of the insulating
film for printed wiring boards is preferably 10 .mu.m. The upper
limit of the average thickness is preferably 2 mm, more preferably
1 mm, and still more preferably 0.5 mm. When the average thickness
is less than the lower limit, sufficient film strength may not be
ensured. On the other hand, when the average thickness is greater
than the upper limit, it may be difficult to apply the film to
electronic devices which are desired to be thinner.
EXAMPLES
[0132] Hereinafter, the embodiments of the present invention will
be described in detail by way of Examples, but the present
invention is not in any way limited to the Examples.
.sup.1H-NMR Analysis
[0133] The .sup.1H-NMR analysis of the polymer was conducted in a
deuterochloroform solvent by using a nuclear magnetic resonance
spectrometer ("ECX400P" available from JEOL, Ltd.).
Synthesis of Polymer
Example 1
[0134] Into a four-neck separable flask equipped with a stirrer,
1-1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (18.6 g, 60.0
mmol), 4,6-dichloropyrimidine (8.9 g, 60.0 mmol), and potassium
carbonate (11.1 g, 81.0 mmol) were weighed. Thereafter,
N-methyl-2-pyrrolidone (64 g) was added thereto, and a reaction was
allowed in a nitrogen atmosphere at 130.degree. C. for 6 hrs. After
the completion of the reaction, the mixture was diluted with
N-methyl-2-pyrrolidone (368 g), the salt was removed therefrom by
filtration, and then the resulting solution was charged into
methanol (9.1 kg). The precipitated solid was filtered off, washed
with a small amount of methanol, collected by filtration, and then
dried by using a vacuum drier under a reduced pressure at
120.degree. C. for 12 hrs, whereby a polymer of Example 1
represented by the following formula (10) was obtained (amount of
polymer obtained: 20.5 g, yield: 90%). A .sup.1H-NMR spectrum of
the polymer thus obtained is shown in FIGURE.
##STR00016##
Example 2
[0135] Into a four-neck separable flask equipped with a stirrer,
1-1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (9.3 g, 30.0
mmol), 4-t-butylcatechol (5.0 g, 30.0 mmol), 4,6-dichloropyrimidine
(8.9 g, 60.0 mmol), and potassium carbonate (11.2 g, 81.0 mmol)
were weighed. Thereafter, N-methyl-2-pyrrolidone (109 g) and
toluene (46 g) were added thereto and a mixture thus obtained was
stirred. After refluxing toluene in a nitrogen atmosphere at
100.degree. C. for 2 hrs, the toluene was removed by distillation,
and then a reaction was further allowed at 130.degree. C. for 6
hrs. After the completion of the reaction, the mixture was diluted
with N-methyl-2-pyrrolidone (249 g), the salt was removed therefrom
by filtration, and then the resulting solution was charged into
methanol (7.5 kg). The precipitated solid was filtered off, washed
with a small amount of methanol, collected by filtration, and then
dried by using a vacuum drier under a reduced pressure at
120.degree. C. for 12 hrs, whereby a polymer of Example 2
represented by the following formula (11) was obtained (amount of
polymer obtained: 8.8 g, yield: 46.7%).
##STR00017##
Example 3
[0136] Into a four-neck separable flask equipped with a stirrer,
2-t-butylhydroquinone (5.8 g, 35.0 mmol),
2,5-di-t-butylhydroquinone (7.8 g, 35.0 mmol),
2,2-bis(4-hydroxyphenyl)propane (6.8 g, 30.0 mmol),
4,6-dichloropyrimidine (14.9 g, 100.0 mmol), and potassium
carbonate (18.7 g, 135.0 mmol) were weighted. Thereafter,
N-methyl-2-pyrrolidone (102.9 g) was added thereto, and a reaction
was allowed in a nitrogen atmosphere at 130.degree. C. for 6 hrs.
After the completion of the reaction, the mixture was diluted with
N-methyl-2-pyrrolidone (300 g), the salt was removed therefrom by
filtration, and then the resulting solution was charged into
methanol (6 kg). The precipitated solid was filtered off, washed
with a small amount of methanol, collected by filtration, and then
dried by using a vacuum drier under a reduced pressure at
120.degree. C. for 12 hrs, whereby a polymer of Example 3
represented by the following formula (12) was obtained (amount of
polymer obtained: 23.4 g, yield: 83.5%).
##STR00018##
Example 4
[0137] Into a four-neck separable flask equipped with a stirrer,
1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (20.3
g, 60.0 mmol), 2,5-di-t-butylhydroquinone (8.9 g, 40.0 mmol),
4,6-dichloropyrimidine (14.9 g, 100.0 mmol), and potassium
carbonate (18.7 g, 135.0 mmol) were weighed. Thereafter,
N-methyl-2-pyrrolidone (102.9 g) was added thereto, and a reaction
was allowed in a nitrogen atmosphere at 130.degree. C. for 6 hrs.
After the completion of the reaction, the mixture was diluted with
N-methyl-2-pyrrolidone (206 g), the salt was removed therefrom by
filtration, and then the resulting solution was charged into
methanol (7 kg). The precipitated solid was filtered off, washed
with a small amount of methanol, collected by filtration, and then
dried by using a vacuum drier under a reduced pressure at
120.degree. C. for 12 hrs, whereby a polymer of Example 4
represented by the following formula (13) was obtained (amount of
polymer obtained: 30.3 g, yield: 82%).
##STR00019##
Example 5
[0138] Into a four-neck separable flask equipped with a stirrer,
1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (25.4
g, 75.0 mmol), 4,6-dichloropyrimidine (11.2 g, 75.0 mmol), and
potassium carbonate (14.0 g, 101.3 mmol) were weighed. Thereafter,
N-methyl-2-pyrrolidone (85 g) was added thereto, and a reaction was
allowed in a nitrogen atmosphere at 130.degree. C. for 6 hrs. After
the completion of the reaction, the mixture was diluted with
N-methyl-2-pyrrolidone (300 g), the salt was removed therefrom by
filtration, and then the resulting solution was charged into
methanol (6 kg). The precipitated solid was filtered off, washed
with a small amount of methanol, collected by filtration, and then
dried by using a vacuum drier under a reduced pressure at
120.degree. C. for 12 hrs, whereby a polymer of Example 5
represented by the following formula (14) was obtained (amount of
polymer obtained: 29.6 g, yield: 95%).
##STR00020##
Example 6
[0139] Into a four-neck separable flask equipped with a stirrer,
1-1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (10.7 g, 34.5
mmol), 3,6-dichloropyridazine (5.1 g, 34.2 mmol), and potassium
carbonate (6.5 g, 47.0 mmol) were weighed. Thereafter,
N-methyl-2-pyrrolidone (36 g) was added thereto, and a reaction was
allowed in a nitrogen atmosphere at 145.degree. C. for 9 hrs. After
the completion of the reaction, the mixture was diluted with
N-methyl-2-pyrrolidone (150 g), the salt was removed therefrom by
filtration, and then the resulting solution was charged into
methanol (3 kg). The precipitated solid was filtered off, washed
with a small amount of methanol, collected by filtration, and then
dried by using a vacuum drier under a reduced pressure at
120.degree. C. for 12 hrs, whereby a polymer of Example 6
represented by the following formula (15) was obtained (amount of
polymer obtained: 7.6 g, yield: 48%).
##STR00021##
Example 7
[0140] Into a four-neck separable flask equipped with a stirrer,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (23.3 g, 75.1
mmol), 2,6-dichloropyrazine (11.2 g, 75.2 mmol), and potassium
carbonate (14.0 g, 101.3 mmol) were weighed. Thereafter,
N-methyl-2-pyrrolidone (80 g) was added thereto, and a reaction was
allowed in a nitrogen atmosphere at 145.degree. C. for 6 hrs. After
the completion of the reaction, the mixture was diluted with
N-methyl-2-pyrrolidone (300 g), the salt was removed therefrom by
filtration, and then the resulting solution was charged into
methanol (6 kg). The precipitated solid was filtered off, washed
with a small amount of methanol, collected by filtration, and then
dried by using a vacuum drier under a reduced pressure at
100.degree. C. for 12 hrs, whereby a polymer of Example 7
represented by the following formula (16) was obtained (amount of
polymer obtained: 21.1 g, yield: 73%).
##STR00022##
Example 8
[0141] Into a four-neck separable flask equipped with a stirrer,
1-1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (37.2 g, 120.0
mmol), 4,6-dichloropyrimidine (17.8 g, 120.0 mmol), and potassium
carbonate (22.2 g, 162.0 mmol) were weighed. Thereafter,
N-methyl-2-pyrrolidone (130 g) was added thereto, and a reaction
was allowed in a nitrogen atmosphere at 130.degree. C. for 10 hrs.
After the completion of the reaction, the mixture was diluted with
N-methyl-2-pyrrolidone (730 g), the salt was removed therefrom by
filtration, and then the resulting solution was charged into
methanol (18 kg). The precipitated solid was filtered off, washed
with a small amount of methanol, collected by filtration, and then
dried by using a vacuum drier under a reduced pressure at
120.degree. C. for 12 hrs, whereby a polymer of Example 8 was
obtained (amount of polymer obtained: 21.6 g, yield: 95%,
represented by the same structural formula as the above formula
(10)).
Comparative Example 1
[0142] Into a four-neck separable flask equipped with a stirrer,
9,9-bis(4-hydroxy-3-methylphenyl)fluorene (18.9 g, 50.0 mmol),
4,6-dichloropyrimidine (7.4 g, 50.0 mmol), and potassium carbonate
(9.3 g, 67.5 mmol) were weighed. Thereafter, N-methyl-2-pyrrolidone
(103 g) was added thereto, and a reaction was allowed in a nitrogen
atmosphere at 130.degree. C. for 6 hrs. After the completion of the
reaction, the mixture was diluted with N-methyl-2-pyrrolidone (329
g), the salt was removed therefrom by filtration, and then the
resulting solution was charged into methanol (9.1 kg). The
precipitated solid was filtered off, washed with a small amount of
methanol, collected by filtration, and then dried by using a vacuum
drier under a reduced pressure at 120.degree. C. for 12 hrs,
whereby a polymer of Comparative Example 1 represented by the
following formula (20) was obtained (amount of polymer obtained:
11.5 g, yield: 61.8%).
##STR00023##
Comparative Example 2
[0143] Into a four-neck separable flask equipped with a stirrer,
1,3-dihydroxybenzene (11.0 g, 100.0 mmol), 4,6-dichloropyrimidine
(14.9 g, 100.0 mmol), and potassium carbonate (18.6 g, 135.0 mmol)
were weighed. Thereafter, N-methyl-2-pyrrolidone (128 g) was added
thereto, and a reaction was allowed in a nitrogen atmosphere at
130.degree. C. for 6 hrs. After the completion of the reaction, the
mixture was diluted with N-methyl-2-pyrrolidone (225 g), the salt
was removed therefrom by filtration, and then the resulting
solution was charged into methanol (7.4 kg). The precipitated solid
was filtered off, washed with a small amount of methanol, collected
by filtration, and then dried by using a vacuum drier under a
reduced pressure at 120.degree. C. for 12 hrs, whereby a polymer of
Comparative Example 2 represented by the following formula (21) was
obtained (amount of polymer obtained: 11.5 g, yield: 62%).
##STR00024##
Comparative Example 3
[0144] Into a four-neck separable flask equipped with a stirrer,
2,2-bis(4-hydroxyphenyl)propane (11.4 g, 50.0 mmol),
4,6-dichloropyrimidine (7.4 g, 50.0 mmol), and potassium carbonate
(9.3 g, 67.5 mmol) were weighed. Thereafter, N-methyl-2-pyrrolidone
(90 g) was added thereto, and a reaction was allowed in a nitrogen
atmosphere at 130.degree. C. for 6 hrs. After the completion of the
reaction, the mixture was diluted with N-methyl-2-pyrrolidone (200
g), the salt was removed therefrom by filtration, and then the
resulting solution was charged into methanol (6.1 kg). The
precipitated solid was filtered off, washed with a small amount of
methanol, collected by filtration, and then dried by using a vacuum
drier under a reduced pressure at 120.degree. C. for 12 hrs,
whereby a polymer of Comparative Example 3 represented by the
following formula (22) was obtained (amount of polymer obtained:
12.1 g, yield: 80%).
##STR00025##
Comparative Example 4
[0145] Into a four-neck separable flask equipped with a stirrer,
1-1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (15.5 g, 50.0
mmol), 4,4'-dichlorodiphenyl sulfone (14.4 g, 50.0 mmol), and
potassium carbonate (9.3 g, 67.5 mmol) were weighed. Thereafter,
N-methyl-2-pyrrolidone (121 g) and toluene (50 g) were added
thereto and a mixture thus obtained was stirred. After refluxing
toluene in a nitrogen atmosphere at 100.degree. C. for 2 hrs, the
toluene was removed by distillation, and then a reaction was
allowed at 190.degree. C. for 6 hrs. After the completion of the
reaction, the mixture was diluted with N-methyl-2-pyrrolidone (398
g), the salt was removed therefrom by filtration, and then the
resulting solution was charged into methanol (10.5 kg). The
precipitated solid was filtered off, washed with a small amount of
methanol, collected by filtration, and then dried by using a vacuum
drier under a reduced pressure at 120.degree. C. for 12 hrs,
whereby a polymer of Comparative Example 4 represented by the
following formula (23) was obtained (amount of polymer obtained:
23.3 g, yield: 88.8%).
##STR00026##
Evaluations
[0146] According to the following methods, the weight average
molecular weight (Mw), the glass transition temperature (Tg), the
1% mass reduction temperature (Td1), the solubility in various
types of organic solvents, the relative permittivity ( r) and the
dielectric loss tangent (tan .delta.) of the polymers thus obtained
were evaluated. The results of the evaluations are shown in Table
1. It is to be noted that "-" in Table 1 means that no evaluation
was made in regard to the evaluation item concerned.
Weight Average Molecular Weight (Mw)
[0147] The weight average molecular weight (Mw) of each polymer was
determined by using a GPC apparatus ("HLC-8320 GPC" available from
Tosoh Corporation) under the following conditions.
[0148] Column: "TSKgel .alpha.-M" coupled to "TSKgel Guard Column
.alpha." (each available from Tosoh Corporation)
[0149] Developing solvent: N-methyl-2-pyrrolidone
[0150] Column temperature: 40.degree. C.
[0151] Flow rate: 1.0 mL/min
[0152] Concentration of sample: 0.75% by mass
[0153] Amount of injected sample: 50 .mu.L
[0154] Detector: differential refractometer
[0155] Standard substance: monodisperse polystyrene
Glass Transition Temperature (Tg)
[0156] The temperature corresponding to a point of intersection of
a baseline and a tangent line through an inflection point which
were drawn with respect to a DSC temperature rise curve in the
thermogram obtained by a differential scanning calorimeter ("Thermo
Plus DSC8230" available from Rigaku Corporation) in a nitrogen
atmosphere at a temperature rise rate of 20.degree. C./min was
defined as the glass transition temperature (Tg) of each polymer.
The temperature corresponding to a peak in a DDSC curve, which is a
curve obtained by differentiating the DSC temperature rise curve,
was defined as the inflection point. The DSC baseline was
determined with appropriate references to the DDSC curve.
1% Mass Reduction Temperature (Td1)
[0157] The temperature at which the mass of the polymer was reduced
by 1% by mass in total on the basis of a thermal mass curve
obtained in a nitrogen atmosphere at a temperature rise rate of
10.degree. C./min by using a differential-type differential thermal
balance ("TG/DTA6200" available from SII NanoTechnology Inc.) was
defined as the 1% mass reduction temperature (Td1) of each polymer.
It is to be noted that Td1 is one of the indices of heat
resistance, and the polymer having a greater value of Td1 is
evaluated to have superior heat resistance.
Solubility in Various Types of Organic Solvents
[0158] The solubility of each polymer in various types of solvents
was determined by adding each polymer to various types of organic
solvents shown in Table 1 to obtain solutions each containing the
polymer at a 10% mass concentration and by stirring the resulting
solutions, and was evaluated as being: "A" in a case where no
precipitates were visually observed; and "B" in a case where
precipitates were visually observed.
[0159] The organic solvents used to evaluate the solubility are
listed below.
[0160] EDM: diethylene glycol ethyl methyl ether
[0161] MMP: methyl 3-methoxypropionate
[0162] BuOAc: butyl acetate
[0163] PGMEA: propylene glycol-1-monomethyl ether-2-acetate
[0164] GBL: .gamma.-butyrolactone
Relative Permittivity ( r) and Dielectric Loss Tangent (Tan
.delta.)
[0165] First, an appropriate amount of each polymer was dissolved
in methylene chloride to prepare a polymer solution, and the
resulting solution was formed into a film on a glass plate and
dried overnight under a normal pressure at room temperature. Then,
remaining methylene chloride was removed by using a vacuum drier to
obtain a film having a size of 3.times.4 cm and an average
thickness of 90 .mu.m. Aluminum was deposited in a vacuum onto one
face of the film by using a vacuum evaporator ("JEE-420" available
from JEOL, Ltd.) to form an electrode, whereby a test piece for
evaluating r and tan .delta. was obtained. In regard to the test
piece, r and tan .delta. were measured by using a precision LCR
meter ("4284A precision LCR meter" available from Hewlett Packard
Inc.) in accordance with JIS-C-2138 (2007), with an amplitude of
100 mV, at a frequency of 1 MHz, at a temperature of 25.degree. C.,
and at a relative humidity of 50%.
TABLE-US-00001 TABLE 1 Structure of Tg Td1 Solubility in each
organic solvent polymer Mw (.degree. C.) (.degree. C.) EDM MMP
BuOAc PGMEA GBL r tan.delta. Example 1 (10) 32,000 206 417 A A B B
A 2.92 0.0083 Example 2 (11) 48,000 183 383 A A A A A 2.88 0.0037
Example 3 (12) 70,000 171 430 A A A A A 2.89 0.0047 Example 4 (13)
80,000 196 412 B B B B B 2.55 0.0020 Example 5 (14) 63,000 197 411
A A A A B 2.75 0.0026 Example 6 (15) 51,800 231 373 A B B B B 3.65
0.0412 Example 7 (16) 11,000 167 377 A A A A A -- -- Example 8 (10)
180,000 -- -- -- -- -- -- -- -- -- Comparative (20) 20,000 240 383
B B B B A -- -- Example 1 Comparative (21) 7,000 -- -- B B B B B --
-- Example 2 Comparative (22) 36,000 153 430 B B B B A 3.10 0.0092
Example 3 Comparative (23) 43,000 233 453 A B B B B 3.08 0.0430
Example 4
[0166] As is clear from Table 1, the polymers of Examples exhibited
superior heat resistance and increased solubility in various types
of organic solvents. In particular, the polymers of Examples 1 to
3, 5, and 7 each had a greater value of Td1, which was no less than
370.degree. C., and each of the polymers was soluble in three or
more different types of the organic solvents (rated A). On the
other hand, each of the polymers of Comparative Examples 1, 3, and
4 was soluble in only one type of the organic solvent, and the
polymer of Comparative Example 2 was soluble in none of the above
organic solvents (rated B).
[0167] Moreover, as shown in Table 1, r and tan .delta. of each of
the polymers of Examples 1 to 5 were smaller than r and tan .delta.
of each of the polymers of Comparative Examples 3 and 4, and it was
thus revealed that the high frequency wave properties of the
printed wiring board containing any of the polymers of Examples 1
to 5 can be improved.
[0168] The present invention is capable of providing a polymer
having superior heat resistance and increased solubility in various
types of organic solvents, and providing a resin composition and a
resin molded product containing the polymer.
[0169] Obviously, numerous modifications and variations of the
present invention are possible in light of the above teachings. It
is therefore to be understood that within the scope of the appended
claims, the invention may be practiced otherwise than as
specifically described herein.
* * * * *