U.S. patent application number 13/415180 was filed with the patent office on 2012-08-16 for cellulose acylate film, retardation film, polarizer and liquid crystal display device.
This patent application is currently assigned to FUJIFILM Corporation. Invention is credited to Masato Nagura, Takayasu Yasuda.
Application Number | 20120204757 13/415180 |
Document ID | / |
Family ID | 43780681 |
Filed Date | 2012-08-16 |
United States Patent
Application |
20120204757 |
Kind Code |
A1 |
Nagura; Masato ; et
al. |
August 16, 2012 |
Cellulose Acylate Film, Retardation Film, Polarizer and Liquid
Crystal Display Device
Abstract
A cellulose acylate film comprising a cellulose acylate resin
satisfying the formulae (i)-(iii) and a compound capable of forming
a hydrogen bond satisfying conditions (A)-(C): (A) the compound has
both a hydrogen bond donor moiety and a hydrogen bond acceptor
moiety in the molecule, (B) the value obtained by dividing the
molecular weight of the compound by the total of the number of the
hydrogen bond donor moiety and the number of the hydrogen bond
acceptor moiety is from 30 to 65, (C) the number of aromatic ring
structures is from 1 to 3, 0.5.ltoreq.A+B.ltoreq.2.7, (i)
0.0.ltoreq.A.ltoreq.2.5, and (ii) 0.1.ltoreq.B.ltoreq.2.0, (iii)
wherein A means the degree of substitution with an acetyl group,
and B means a total of the degree of substitution with a propionyl
group and the degree of substitution with a butyryl group.
Inventors: |
Nagura; Masato;
(Minami-ashigara-shi, JP) ; Yasuda; Takayasu;
(Minami-ashigara-shi, JP) |
Assignee: |
FUJIFILM Corporation
Minato-ku
JP
|
Family ID: |
43780681 |
Appl. No.: |
13/415180 |
Filed: |
March 8, 2012 |
Current U.S.
Class: |
106/170.1 |
Current CPC
Class: |
C09K 19/54 20130101;
G02F 1/133634 20130101; C09K 2019/0492 20130101; G02F 2001/133635
20130101; Y10T 428/1036 20150115; G02B 5/3083 20130101; G02B 1/04
20130101; C09K 2323/03 20200801 |
Class at
Publication: |
106/170.1 |
International
Class: |
C08L 1/14 20060101
C08L001/14 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 29, 2009 |
JP |
2009-225478 |
Claims
1. A cellulose acylate film comprising a cellulose acylate resin
having a degree of acyl substitution satisfying all the following
formulae (i), (ii) and (iii) and a compound capable of forming a
hydrogen bond satisfying all the following conditions (A), (B) and
(C): (A) the compound has both a hydrogen bond donor moiety and a
hydrogen bond acceptor moiety in the molecule, (B) the value
obtained by dividing the molecular weight of the compound by the
total of the number of the hydrogen bond donor moiety and the
number of the hydrogen bond acceptor moiety is from 30 to 65, (C)
the number of aromatic ring structures is from 1 to 3,
0.5.ltoreq.A+B.ltoreq.2.7, (i) 0.0.ltoreq.A.ltoreq.2.5, and (ii)
0.1.ltoreq.B.ltoreq.2.0, (iii) where, in the formulae (i), (ii) and
(iii), A means the degree of substitution with an acetyl group, and
B means a total of the degree of substitution with a propionyl
group and the degree of substitution with a butyryl group, wherein
the compound capable of forming a hydrogen bond is represented by
the following formula (G-1): ##STR00095## wherein L.sup.1
represents a single bond or a divalent linking group having a
hetero atom; and R.sup.81 represents a hydrogen atom, an alkyl
group having from 1 to 20 carbon atoms, an alkenyl group having
from 2 to 20 carbon atoms, an alkynyl group having from 2 to 20
carbon atoms, an aryl group having from 6 to 20 carbon atoms or an
arylalkyl group having from 7 to 20 carbon atoms.
2. The cellulose acylate film according to claim 1, wherein the
degree of substitution with an acyl group of the cellulose acylate
satisfies all the following formulae (iv), (v) and (vi):
1.0.ltoreq.A+B.ltoreq.2.5, (iv) 0.1.ltoreq.A.ltoreq.2.0, and (v)
0.1.ltoreq.B.ltoreq.1.8, (vi) where, in the formulae (iv), (v) and
(vi), A means the degree of substitution with an acetyl group, and
B means a total of the degree of substitution with a propionyl
group and the degree of substitution with a butyryl group.
3. The cellulose acylate film according to claim 1, wherein the
degree of substitution with an acyl group of the cellulose acylate
satisfies all the following formulae (vii), (viii) and (ix):
1.2.ltoreq.A+B.ltoreq.2.5, (vii) 0.1.ltoreq.A.ltoreq.1.9, and
(viii) 0.5.ltoreq.B.ltoreq.1.8, (ix) where, in the formulae (vii),
(viii) and (ix), A means the degree of substitution with an acetyl
group, and B means a total of the degree of substitution with a
propionyl group and the degree of substitution with a butyryl
group.
4. The cellulose acylate film according to claim 1, wherein the
cellulose acylate resin has a mass-average degree of polymerization
of from 350 to 800.
5. The cellulose acylate film according to claim 1, wherein the
hydrogen bond donor moiety is connected to the hydrogen bond
acceptor moiety through from 0 to 3 atoms.
6. The cellulose acylate film according to claim 1, wherein the
compound capable of forming a hydrogen bond has a molecular weight
of from 100 to 1000.
7. The cellulose acylate film according to claim 1, wherein the
content of the compound capable of forming a hydrogen bond is 30%
by mass or less relative to the content of the cellulose acylate
resin.
8. A retardation film comprising a cellulose acylate film, wherein
the cellulose acylate film comprises a cellulose acylate resin
having a degree of acyl substitution satisfying all the following
formulae (i), (ii) and (iii) and a compound capable of forming a
hydrogen bond satisfying all the following conditions (A), (B) and
(C): (A) the compound has both a hydrogen bond donor moiety and a
hydrogen bond acceptor moiety in the molecule, (B) the value
obtained by dividing the molecular weight of the compound by the
total of the number of the hydrogen bond donor moiety and the
number of the hydrogen bond acceptor moiety is from 30 to 65, (C)
the number of aromatic ring structures is from 1 to 3,
0.5.ltoreq.A+B.ltoreq.2.7, (i) 0.0.ltoreq.A.ltoreq.2.5, and (ii)
0.1.ltoreq.B.ltoreq.2.0, (iii) where, in the formulae (i), (ii) and
(iii), A means the degree of substitution with an acetyl group, and
B means a total of the degree of substitution with a propionyl
group and the degree of substitution with a butyryl group, wherein
the compound capable of forming a hydrogen bond is represented by
the following formula (G-1): ##STR00096## wherein L.sup.1
represents a single bond or a divalent linking group having a
hetero atom; and R.sup.81 represents a hydrogen atom, an alkyl
group having from 1 to 20 carbon atoms, an alkenyl group having
from 2 to 20 carbon atoms, an alkynyl group having from 2 to 20
carbon atoms, an aryl group having from 6 to 20 carbon atoms or an
arylalkyl group having from 7 to 20 carbon atoms.
9. A polarizer comprising a cellulose acylate film, wherein the
cellulose acylate film comprises a cellulose acylate resin having a
degree of acyl substitution satisfying all the following formulae
(i), (ii) and (iii) and a compound capable of forming a hydrogen
bond satisfying all the following conditions (A), (B) and (C): (A)
the compound has both a hydrogen bond donor moiety and a hydrogen
bond acceptor moiety in the molecule, (B) the value obtained by
dividing the molecular weight of the compound by the total of the
number of the hydrogen bond donor moiety and the number of the
hydrogen bond acceptor moiety is from 30 to 65, (C) the number of
aromatic ring structures is from 1 to 3, 0.5.ltoreq.A+B.ltoreq.2.7,
(i) 0.0.ltoreq.A.ltoreq.2.5, and (ii) 0.1.ltoreq.B.ltoreq.2.0,
(iii) where, in the formulae (i), (ii) and (iii), A means the
degree of substitution with an acetyl group, and B means a total of
the degree of substitution with a propionyl group and the degree of
substitution with a butyryl group, wherein the compound capable of
forming a hydrogen bond is represented by the following formula
(G-1): ##STR00097## wherein L.sup.1 represents a single bond or a
divalent linking group having a hetero atom; and R.sup.81
represents a hydrogen atom, an alkyl group having from 1 to 20
carbon atoms, an alkenyl group having from 2 to 20 carbon atoms, an
alkynyl group having from 2 to 20 carbon atoms, an aryl group
having from 6 to 20 carbon atoms or an arylalkyl group having from
7 to 20 carbon atoms.
10. A liquid crystal display device comprising a cellulose acylate
film, wherein the cellulose acylate film comprises a cellulose
acylate resin having a degree of acyl substitution satisfying all
the following formulae (i), (ii) and (iii) and a compound capable
of forming a hydrogen bond satisfying all the following conditions
(A), (B) and (C): (A) the compound has both a hydrogen bond donor
moiety and a hydrogen bond acceptor moiety in the molecule, (B) the
value obtained by dividing the molecular weight of the compound by
the total of the number of the hydrogen bond donor moiety and the
number of the hydrogen bond acceptor moiety is from 30 to 65, (C)
the number of aromatic ring structures is from 1 to 3,
0.5.ltoreq.A+B.ltoreq.2.7, (i) 0.0.ltoreq.A.ltoreq.2.5, and (ii)
0.1.ltoreq.B.ltoreq.2.0, (iii) where, in the formulae (i), (ii) and
(iii), A means the degree of substitution with an acetyl group, and
B means a total of the degree of substitution with a propionyl
group and the degree of substitution with a butyryl group, wherein
the compound capable of forming a hydrogen bond is represented by
the following formula (G-1): ##STR00098## wherein L.sup.1
represents a single bond or a divalent linking group having a
hetero atom; and R.sup.81 represents a hydrogen atom, an alkyl
group having from 1 to 20 carbon atoms, an alkenyl group having
from 2 to 20 carbon atoms, an alkynyl group having from 2 to 20
carbon atoms, an aryl group having from 6 to 20 carbon atoms or an
arylalkyl group having from 7 to 20 carbon atoms.
11. A cellulose acylate film comprising a cellulose acylate resin
having a degree of acyl substitution satisfying all the following
formulae (i), (ii) and (iii) and a compound capable of forming a
hydrogen bond satisfying all the following conditions (A), (B) and
(C): (A) the compound has both a hydrogen bond donor moiety and a
hydrogen bond acceptor moiety in the molecule, (B) the value
obtained by dividing the molecular weight of the compound by the
total of the number of the hydrogen bond donor moiety and the
number of the hydrogen bond acceptor moiety is from 30 to 65, (C)
the number of aromatic ring structures is from 1 to 3,
0.5.ltoreq.A+B.ltoreq.2.7, (i) 0.0.ltoreq.A.ltoreq.2.5, and (ii)
0.1.ltoreq.B.ltoreq.2.0, (iii) where, in the formulae (i), (ii) and
(iii), A means the degree of substitution with an acetyl group, and
B means a total of the degree of substitution with a propionyl
group and the degree of substitution with a butyryl group, wherein
the compound capable of forming a hydrogen bond is represented by
the following formula (H-1): ##STR00099## wherein L.sup.3
represents a single bond or a divalent linking group having a
hetero atom; and R.sup.85 represents an alkyl group having from 1
to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon
atoms, an alkynyl group having from 2 to 20 carbon atoms, an aryl
group having from 6 to 20 carbon atoms or an arylalkyl group having
from 7 to 20 carbon atoms; R.sup.83 and R.sup.84 each independently
represent a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group; and X.sup.53
and X.sup.54 each independently represent any one selected from the
group of divalent linking groups of the following formula (P):
##STR00100## wherein the side * is the linking site to the N atom
that bonds to the heterocyclic ring in the compound of the formula
(H-1).
12. The cellulose acylate film according to claim 11, wherein the
degree of substitution with an acyl group of the cellulose acylate
satisfies all the following formulae (iv), (v) and (vi):
1.0.ltoreq.A+B.ltoreq.2.5, (iv) 0.1.ltoreq.A.ltoreq.2.0, and (v)
0.1.ltoreq.B.ltoreq.1.8, (vi) where, in the formulae (iv), (v) and
(vi), A means the degree of substitution with an acetyl group, and
B means a total of the degree of substitution with a propionyl
group and the degree of substitution with a butyryl group.
13. The cellulose acylate film according to claim 11, wherein the
degree of substitution with an acyl group of the cellulose acylate
satisfies all the following formulae (vii), (viii) and (ix):
1.2.ltoreq.A+B.ltoreq.2.5, (vii) 0.1.ltoreq.A.ltoreq.1.9, and
(viii) 0.5.ltoreq.B.ltoreq.1.8, (ix) where, in the formulae (vii),
(viii) and (ix), A means the degree of substitution with an acetyl
group, and B means a total of the degree of substitution with a
propionyl group and the degree of substitution with a butyryl
group.
14. The cellulose acylate film according to claim 11, wherein the
cellulose acylate resin has a mass-average degree of polymerization
of from 350 to 800.
15. The cellulose acylate film according to claim 11, wherein the
hydrogen bond donor moiety is connected to the hydrogen bond
acceptor moiety through from 0 to 3 atoms.
16. The cellulose acylate film according to claim 11, wherein the
compound capable of forming a hydrogen bond has a molecular weight
of from 100 to 1000.
17. The cellulose acylate film according to claim 11, wherein the
content of the compound capable of forming a hydrogen bond is 30%
by mass or less relative to the content of the cellulose acylate
resin.
18. A retardation film comprising a cellulose acylate film, wherein
the cellulose acylate film comprises a cellulose acylate resin
having a degree of acyl substitution satisfying all the following
formulae (i), (ii) and (iii) and a compound capable of forming a
hydrogen bond satisfying all the following conditions (A), (B) and
(C): (A) the compound has both a hydrogen bond donor moiety and a
hydrogen bond acceptor moiety in the molecule, (B) the value
obtained by dividing the molecular weight of the compound by the
total of the number of the hydrogen bond donor moiety and the
number of the hydrogen bond acceptor moiety is from 30 to 65, (C)
the number of aromatic ring structures is from 1 to 3,
0.5.ltoreq.A+B.ltoreq.2.7, (i) 0.0.ltoreq.A.ltoreq.2.5, and (ii)
0.1.ltoreq.B.ltoreq.2.0, (iii) where, in the formulae (i), (ii) and
(iii), A means the degree of substitution with an acetyl group, and
B means a total of the degree of substitution with a propionyl
group and the degree of substitution with a butyryl group, wherein
the compound capable of forming a hydrogen bond is represented by
the following formula (H-1): ##STR00101## wherein L.sup.3
represents a single bond or a divalent linking group having a
hetero atom; and R.sup.85 represents an alkyl group having from 1
to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon
atoms, an alkynyl group having from 2 to 20 carbon atoms, an aryl
group having from 6 to 20 carbon atoms or an arylalkyl group having
from 7 to 20 carbon atoms; R.sup.83 and R.sup.84 each independently
represent a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group; and X.sup.53
and X.sup.54 each independently represent any one selected from the
group of divalent linking groups of the following formula (P):
##STR00102## wherein the side * is the linking site to the N atom
that bonds to the heterocyclic ring in the compound of the formula
(H-1).
19. A polarizer comprising a cellulose acylate film, wherein the
cellulose acylate film comprises a cellulose acylate resin having a
degree of acyl substitution satisfying all the following formulae
(i), (ii) and (iii) and a compound capable of forming a hydrogen
bond satisfying all the following conditions (A), (B) and (C): (A)
the compound has both a hydrogen bond donor moiety and a hydrogen
bond acceptor moiety in the molecule, (B) the value obtained by
dividing the molecular weight of the compound by the total of the
number of the hydrogen bond donor moiety and the number of the
hydrogen bond acceptor moiety is from 30 to 65, (C) the number of
aromatic ring structures is from 1 to 3, 0.5.ltoreq.A+B.ltoreq.2.7,
(i) 0.0.ltoreq.A.ltoreq.2.5, and (ii) 0.1.ltoreq.B.ltoreq.2.0,
(iii) where, in the formulae (i), (ii) and (iii), A means the
degree of substitution with an acetyl group, and B means a total of
the degree of substitution with a propionyl group and the degree of
substitution with a butyryl group, wherein the compound capable of
forming a hydrogen bond is represented by the following formula
(H-1): ##STR00103## wherein L.sup.3 represents a single bond or a
divalent linking group having a hetero atom; and R.sup.85
represents an alkyl group having from 1 to 20 carbon atoms, an
alkenyl group having from 2 to 20 carbon atoms, an alkynyl group
having from 2 to 20 carbon atoms, an aryl group having from 6 to 20
carbon atoms or an arylalkyl group having from 7 to 20 carbon
atoms; R.sup.83 and R.sup.84 each independently represent a
hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
a heterocyclic group or an aryl group; and X.sup.53 and X.sup.54
each independently represent any one selected from the group of
divalent linking groups of the following formula (P): ##STR00104##
wherein the side * is the linking site to the N atom that bonds to
the heterocyclic ring in the compound of the formula (H-1).
20. A liquid crystal display device comprising a cellulose acylate
film, wherein the cellulose acylate film comprises a cellulose
acylate resin having a degree of acyl substitution satisfying all
the following formulae (i), (ii) and (iii) and a compound capable
of forming a hydrogen bond satisfying all the following conditions
(A), (B) and (C): (A) the compound has both a hydrogen bond donor
moiety and a hydrogen bond acceptor moiety in the molecule, (B) the
value obtained by dividing the molecular weight of the compound by
the total of the number of the hydrogen bond donor moiety and the
number of the hydrogen bond acceptor moiety is from 30 to 65, (C)
the number of aromatic ring structures is from 1 to 3,
0.5.ltoreq.A+B.ltoreq.2.7, (i) 0.0.ltoreq.A.ltoreq.2.5, and (ii)
0.1.ltoreq.B.ltoreq.2.0, (iii) where, in the formulae (i), (ii) and
(iii), A means the degree of substitution with an acetyl group, and
B means a total of the degree of substitution with a propionyl
group and the degree of substitution with a butyryl group, wherein
the compound capable of forming a hydrogen bond is represented by
the following formula (H-1): ##STR00105## wherein L.sup.3
represents a single bond or a divalent linking group having a
hetero atom; and R.sup.85 represents an alkyl group having from 1
to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon
atoms, an alkynyl group having from 2 to 20 carbon atoms, an aryl
group having from 6 to 20 carbon atoms or an arylalkyl group having
from 7 to 20 carbon atoms; R.sup.83 and R.sup.84 each independently
represent a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group; and X.sup.53
and X.sup.54 each independently represent any one selected from the
group of divalent linking groups of the following formula (P):
##STR00106## wherein the side * is the linking site to the N atom
that bonds to the heterocyclic ring in the compound of the formula
(H-1).
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser.
No. 12/893,378 filed on Sep. 29, 2010, now allowed, which claims
the benefit of priority from Japanese Patent Application No.
225478/2009, filed on Sep. 29, 2009, the contents of each are
herein incorporated by reference in their entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a cellulose acylate film, a
retardation film, a polarizer containing the film and a liquid
crystal display device, especially a VA (vertical aligned)-mode
liquid crystal display device.
[0004] 2. Description of the Related Art
[0005] The display characteristics of liquid crystal display
devices are being improved more and more these days, and in
particular, it is known that, in a VA-mode liquid crystal display
devices that is hopeful for large-sized TVs, two polarizers are
arranged on the panel side and the backlight side of the liquid
crystal display in such a manner that their absorption axes are
perpendicular to each other, and in addition, an optically biaxial
retardation film is arranged between each polarizer and the liquid
crystal cell, thereby realizing a broader viewing angle, or that
is, enhancing the display characteristics of the device.
[0006] As the retardation film of the type, recently, a cellulose
acylate film capable of expressing excellent optical properties,
concretely an in-plane retardation Re(nm) and a thickness-direction
retardation Rth(nm) has become specifically noted and used as a
retardation film in liquid crystal display devices. Among the
cellulose acylate film, a cellulose acetate film is widely
used.
[0007] As a compound that may be added to such a cellulose acetate
film so as to increase Rth of the film, a retardation enhancer
having a specific structure is disclosed (see JP-A 2004-109410).
The retardation enhancer disclosed in this reference is a compound
containing a keto-enol tautomerizable compound as its constitutive
element and capable of forming a molecular complex; and as one
example thereof, the reference discloses a compound having a
1,3,5-triazine ring-containing structure, especially a guanamine
skeleton-having compound. As other compounds capable of being added
to a cellulose acetate film to increase Rth of the film, disclosed
are a retardation enhancer of a discotic compound (see JP-A
2001-166144, 2003-344655). The retardation enhancer disclosed in
these references are discotic compounds and compounds having a
structure containing a 1,3,5-triazine ring or porphyrin skeleton
are exemplified therefor.
SUMMARY OF THE INVENTION
[0008] On the other hand, the present inventors have investigated
the other characteristics of the cellulose acetate film containing
such a retardation enhancer, and have found that Re and Rth of the
film greatly fluctuate depending on the change in the humidity of
the usage environment, or that is, the humidity dependence of Re
and Rth of the film is high. Accordingly, for the purpose of
solving the problems, the inventors have tried using any other
substrate than cellulose acetate. During this, the inventors have
found that some of the retardation enhancers described in JP-A
2004-109410 and 2001-166144 could not be effective for retardation
enhancement for some other substrates. In other words, the
inventors' finding is that the effect of additives varies depending
on the substrate to which they are added.
[0009] Based on this finding, the inventors have further
investigated the influence of various additives on typically
cellulose acylate propionate substrates, and have found that, when
a compound capable of forming a hydrogen bond satisfying the
following conditions (A) to (C) is added to a cellulose acylate
propionate substrate, then the humidity dependence of Re and Rth of
the substrate can be significantly improved and the stability of
the optical properties of the substrate to environmental humidity
change is thereby bettered. Accordingly, the inventors have made
further studies for the purpose of obtaining a compound which, when
added to a cellulose acylate propionate substrate, can
significantly retard the fluctuation of Re and Rth of the substrate
in usage environment humidity change.
(A) the compound has both a hydrogen bond donor moiety and a
hydrogen bond acceptor moiety in the molecule, (B) the value
obtained by dividing the molecular weight of the compound by the
total of the number of the hydrogen bond donor moiety and the
number of the hydrogen bond acceptor moiety is from 30 to 65, and
(C) the number of aromatic ring structures is from 1 to 3.
[0010] Specifically, an object of the invention is to provide a
cellulose acylate film of which the fluctuation of Re and Rth in
usage environment humidity change is retarded. Another object of
the invention is to provide a retardation film comprising the
cellulose acylate film, and a polarizer and a liquid crystal
display device comprising the cellulose acylate film or the
retardation film.
[0011] For the purpose of solving the above-mentioned problems, the
inventors of the present invention have investigated the
substituents that heterocyclic rings can have, and as a result,
have found that a compound having a substituent falling within a
range of a specific substituent group can improve the humidity
dependence of the substrate, and have completed the present
invention.
[0012] In particular, the compound having a specific substituent on
the 1,3,5-triazine ring, which is selected in the invention,
differs from the compounds in JP-A 2001-166144 in which the
compounds were found to have the ability to increase Rth based on
the discotic configuration (or planarity) thereof, in point of the
range selected from among the compounds having a 1,3,5-triazine
ring. Concretely, in the present invention, the inventors have
found that specific 1,3,5-triazine ring-having compounds having a
specific 1,3,5-triazine ring configuration and having a specific
type of substituent on the ring, which are selected from a large
number of 1,3,5-triazine ring-having compounds, can exhibit a novel
effect of retarding the fluctuation of Re and Rth of cellulose
acylate film. Therefore, in the invention, the 1,3,5-triazine
ring-having compounds are not limited to those having a discotic
form as a whole.
[0013] Concretely, the means for solving the above-mentioned
problems of the invention are as follows:
[0014] [1] A cellulose acylate film comprising a cellulose acylate
resin having a degree of acyl substitution satisfying all the
following formulae (i), (ii) and (iii) and a compound capable of
forming a hydrogen bond satisfying all the following conditions
(A), (B) and (C):
[0015] (A) the compound has both a hydrogen bond donor moiety and a
hydrogen bond acceptor moiety in the molecule,
[0016] (B) the value obtained by dividing the molecular weight of
the compound by the total of the number of the hydrogen bond donor
moiety and the number of the hydrogen bond acceptor moiety is from
30 to 65,
[0017] (C) the number of aromatic ring structures is from 1 to
3,
0.5.ltoreq.A+B.ltoreq.2.7, (i)
0.0.ltoreq.A.ltoreq.2.5, and (ii)
0.1.ltoreq.B.ltoreq.2.0, (iii)
where, in the formulae (i), (ii) and (iii), A means the degree of
substitution with an acetyl group, and B means a total of the
degree of substitution with a propionyl group and the degree of
substitution with a butyryl group.
[0018] [2] The cellulose acylate film of [1], wherein the degree of
substitution with an acyl group of the cellulose acylate satisfies
all the following formulae (iv), (v) and (vi):
1.0.ltoreq.A+B.ltoreq.2.5, (iv)
0.1.ltoreq.A.ltoreq.2.0, and (v)
0.1.ltoreq.B.ltoreq.1.8, (vi)
where, in the formulae (iv), (v) and (vi), A means the degree of
substitution with an acetyl group, and B means a total of the
degree of substitution with a propionyl group and the degree of
substitution with a butyryl group.
[0019] [3] The cellulose acylate film of [1] or [2], wherein the
compound capable of forming a hydrogen bond is represented by the
following formula (A-1):
##STR00001##
wherein Ra represents an alkyl group, an alkenyl group, an alkynyl
group, a heterocyclic group or an aryl group; X.sup.1, X.sup.2,
X.sup.3 and X.sup.4 each independently represent a single bond or a
divalent linking group; and R.sup.1, R.sup.2, R.sup.3 and R.sup.4
each independently represent a hydrogen atom, an alkyl group, an
alkenyl group, an alkynyl group, an aryl group or a heterocyclic
group.
[0020] [4] The cellulose acylate film of [1] or [2], wherein the
compound capable of forming a hydrogen bond is represented by the
following formula (B-1):
##STR00002##
wherein Rb and Rc each independently represent an alkyl group, an
alkenyl group, an alkynyl group, a heterocyclic group or an aryl
group; X.sup.5 and X.sup.6 each independently represent a single
bond or a divalent linking group; R.sup.5 and R.sup.6 each
independently represent a hydrogen atom, an alkyl group, an alkenyl
group, an alkynyl group, an aryl group or a heterocyclic group.
[0021] [5] The cellulose acylate film of [3] or [4], wherein
X.sup.1, X.sup.2, X.sup.3 and X.sup.4 in the formula (A-1) and
X.sup.5 and X.sup.6 in the formula (B-1) each independently
represent any one selected from a single bond and the group of
divalent linking groups of the following formula (P):
##STR00003##
wherein the side * is the linking site to the N atom that bonds to
the 1,3,5-triazine ring in the compound of the formula (A-1) or
(B-1).
[0022] [6] The cellulose acylate film of [1] or [2], wherein the
compound capable of forming a hydrogen bond is represented by the
following formula (C-1):
##STR00004##
wherein Ra.sup.11 represents an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group; Rb.sup.11,
Rc.sup.11, Rd.sup.11 and Re.sup.11 each independently represent a
hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
a heterocyclic group or an aryl group; Q.sup.1 represents --O--,
--S-- or --NRf--; Rf represents a hydrogen atom, an alkyl group, an
alkenyl group, an alkynyl group, a heterocyclic group or an aryl
group, and may be taken together with Ra.sup.11 to form a ring;
X.sup.11, X.sup.12 and X.sup.13 each independently represent a
single bond or a divalent linking group; and X.sup.14 represents
any one selected from the group of divalent linking groups of the
following formula (P):
##STR00005##
wherein the side * is the linking site to the N atom that bonds to
the 1,3,5-triazine ring in the compound of the formula (C-1).
[0023] [7] The cellulose acylate film of [1] or [2], wherein the
compound capable of forming a hydrogen bond is represented by the
following formula (D-1):
##STR00006##
wherein Ra.sup.21 and Rg.sup.21 each independently represent an
alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group; Rd.sup.21 and Re.sup.21 each independently
represent a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group; Q.sup.11
represents --O--, --S-- or --NRf--; Rf represents a hydrogen atom,
an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group, and may be taken together with Ra.sup.21 to
form a ring; Q.sup.12 represents --O--, --S-- or --NRh--; Rh
represents a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group, and may be
taken together with Rg.sup.21 to form a ring; X.sup.23 represents a
single bond or a divalent linking group; and X.sup.24 represents
any one selected from the group of divalent linking groups of the
following formula (P):
##STR00007##
wherein the side * is the linking site to the N atom that bonds to
the 1,3,5-triazine ring in the compound of the formula (D-1).
[0024] [8] The cellulose acylate film of [1] or [2], wherein the
compound capable of forming a hydrogen bond is represented by the
following formula (E-1):
##STR00008##
wherein Y.sup.1 represents a methine group or --N--; Ra.sup.31
represents an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group; Rb.sup.31, Rc.sup.31,
Rd.sup.31 and Re.sup.31 each independently represent a hydrogen
atom, an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group; Q.sup.21 represents a single
bond, --O--, --S-- or --NRf--; Rf represents a hydrogen atom, an
alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group, and may be taken together with Ra.sup.31 to
form a ring; X.sup.31, X.sup.32 and X.sup.33 each independently
represent a single bond or a divalent linking group; and X.sup.34
represents any one selected from the group of divalent linking
groups of the following formula (Q):
##STR00009##
wherein the side * is the linking site to the N atom that bonds to
the heterocyclic ring in the compound of the formula (E-1).
[0025] [9] The cellulose acylate film of [1] or [2], wherein the
compound capable of forming a hydrogen bond is represented by the
following formula (F-1):
##STR00010##
wherein Y.sup.11 represents a methine group or --N--; Ra.sup.41 and
Rg.sup.41 each independently represent an alkyl group, an alkenyl
group, an, alkynyl group, a heterocyclic group or an aryl group;
Rd.sup.41 and Re.sup.41 each independently represent a hydrogen
atom, an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group; Q.sup.31 represents --O--,
--S-- or --NRf--; Rf represents a hydrogen atom, an alkyl group, an
alkenyl group, an alkynyl group, a heterocyclic group or an aryl
group, and may be taken together with Ra.sup.41 to form a ring;
Q.sup.32 represents --O--, --S-- or --NRh--; Rh represents a
hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
a heterocyclic group or an aryl group, and may be taken together
with Rg.sup.41 to form a ring; X.sup.43 represents a single bond or
a divalent linking group; and X.sup.44 represents any one selected
from the group of divalent linking groups of the following formula
(P):
##STR00011##
wherein the side * is the linking site to the N atom that bonds to
the heterocyclic ring in the compound of the formula (F-1).
[0026] [10] The cellulose acylate film of [1] or [2], wherein the
compound capable of forming a hydrogen bond is represented by the
following formula (G-1):
##STR00012##
wherein L.sup.1 represents a single bond or a divalent linking
group having a hetero atom; and R.sup.81 represents a hydrogen
atom, an alkyl group having from 1 to 20 carbon atoms, an alkenyl
group having from 2 to 20 carbon atoms, an alkynyl group having
from 2 to 20 carbon atoms, an aryl group having from 6 to 20 carbon
atoms or an arylalkyl group having from 7 to 20 carbon atoms.
[0027] [11] The cellulose acylate film of [1] or [2], wherein the
compound capable of forming a hydrogen bond is represented by the
following formula (H-1):
##STR00013##
wherein L.sup.3 represents a single bond or a divalent linking
group having a hetero atom; and R.sup.85 represents an alkyl group
having from 1 to 20 carbon atoms, an alkenyl group having from 2 to
20 carbon atoms, an alkynyl group having from 2 to 20 carbon atoms,
an aryl group having from 6 to 20 carbon atoms or an arylalkyl
group having from 7 to 20 carbon atoms; R.sup.83 and R.sup.84 each
independently represent a hydrogen atom, an alkyl group, an alkenyl
group, an alkynyl group, a heterocyclic group or an aryl group; and
X.sup.53 and X.sup.54 each independently represent any one selected
from the group of divalent linking groups of the following formula
(P):
##STR00014##
wherein the side * is the linking site to the N atom that bonds to
the heterocyclic ring in the compound of the formula (H-1).
[0028] [12] The cellulose acylate film of any one of [1] to [11],
wherein the compound capable of forming a hydrogen bond has a
molecular weight of from 100 to 1000.
[0029] [13] The cellulose acylate film of any one of [1] to [12],
wherein the content of the compound capable of forming a hydrogen
bond is 30% by mass or less relative to the content of the
cellulose acylate resin.
[0030] [14] A retardation film comprising the cellulose acylate
film of any one of [1] to [13].
[0031] [15] A polarizer comprising the cellulose acylate film of
any one of [1] to [13] or the retardation film of [14].
[0032] [16] A liquid crystal display device comprising the
cellulose acylate film of any one of [1] to [13], the retardation
film of [14] or the polarizer of [15].
[0033] The cellulose acylate film of the invention is capable of
effectively retarding the fluctuation of Re and Rth in humidity
change in the usage environment. It can be therefore preferably
applicable to a retardation film, a polarizer and particularly
preferably a liquid crystal display device of the invention.
BRIEF DESCRIPTION OF THE DRAWING
[0034] FIG. 1 is a schematic view showing the constitution of one
example of the liquid crystal display device of the invention.
[0035] In the drawing, 1 is an upper substrate of liquid crystal
cell, 3 is a lower substrate of liquid crystal cell, 5 is a liquid
crystal layer (liquid crystal molecule), 8a and 8b each are
protective film for polarizer, 9a and 9b each are the absorption
axis of the protective film for polarizer, 10a and 10b each are a
retardation film (cellulose acylate film of the invention), 11a and
11b each are the absorption axis of the retardation film (cellulose
acylate film of the invention), P1 and P2 each are a polarizer, and
LC is a liquid crystal cell.
BEST MODE FOR CARRYING OUT THE INVENTION
[0036] Description will now be made in detail of the invention.
Although the following description of its structural features may
often be made on the basis of typical embodiments of the invention,
it is to be understood that the invention is not limited to any
such embodiment. It is also to be noted that every numerical range
as herein expressed by employing the words "from" and "to", or
simply the word "to", or the symbol "-" is supposed to include the
lower and upper limits thereof as defined by such words or symbol,
unless otherwise noted. In the invention, "mass %" means equal to
"weight %", and "% by mass" means equal to "% by weight".
[0037] First of all, the definition of the terms used in this
specification is described below.
(Retardation (Re(.lamda.) and Rth(.lamda.))
[0038] In this specification, Re(.lamda.) and Rth(.lamda.) are
retardation in plane (nm) and retardation along the thickness
direction (nm), respectively, at a wavelength of .lamda..
Re(.lamda.) is measured by applying light having a wavelength of
.lamda. nm to a film in the normal direction of the film, using
KOBRA 21ADH or WR (by Oji Scientific Instruments).
[0039] When a film to be analyze by a monoaxial or biaxial index
ellipsoid, Rth(.lamda.) of the film is calculated as follows.
[0040] Rth(.lamda.) is calculated by KOBRA 21ADH or WR based on six
Re(.lamda.) values which are measured for incoming light of a
wavelength .lamda. nm in six directions which are decided by a
10.degree. step rotation from 0.degree. to 50.degree. with respect
to the normal direction of a sample film using an in-plane slow
axis, which is decided by KOBRA 21ADH, as an inclination axis (a
rotation axis; defined in an arbitrary in-plane direction if the
film has no slow axis in plane); a value of hypothetical mean
refractive index; and a value entered as a thickness value of the
film.
[0041] In the above, when the film to be analyzed has a direction
in which the retardation value is zero at a certain inclination
angle, around the in-plane slow axis from the normal direction as
the rotation axis, then the retardation value at the inclination
angle larger than the inclination angle to give a zero retardation
is changed to negative data, and then the Rth(.lamda.) of the film
is calculated by KOBRA 21ADH or WR.
[0042] Around the slow axis as the inclination angle (rotation
angle) of the film (when the film does not have a slow axis, then
its rotation axis may be in any in-plane direction of the film),
the retardation values are measured in any desired inclined two
directions, and based on the data, and the estimated value of the
mean refractive index and the inputted film thickness value, Rth
may be calculated according to the following formulae (X) and
(XI):
Re ( .theta. ) = [ nx - ( ny .times. nz ) { ny sin ( sin - 1 ( sin
( - .theta. ) nx ) ) } 2 + { nz cos ( sin - 1 ( sin ( - .theta. )
nx ) ) } 2 ] .times. d cos { sin - 1 ( sin ( - .theta. ) nx ) }
Formula ( X ) Rth = [ nx + ny 2 - nz ] .times. d Formula ( XI )
##EQU00001##
wherein Re(.theta.) represents a retardation value in the direction
inclined by an angle .theta. from the normal direction; nx
represents a refractive index in the in-plane slow axis direction;
ny represents a refractive index in the in-plane direction
perpendicular to nx; and nz represents a refractive index in the
direction perpendicular to nx and ny. And "d" is a thickness of the
sample.
[0043] When the film to be analyzed is not expressed by a monoaxial
or biaxial index ellipsoid, or that is, when the film does not have
an optical axis, then Rth(.lamda.) of the film may be calculated as
follows.
[0044] Re(.lamda.) of the film is measured around the slow axis
(judged by KOBRA 21ADH or WR) as the in-plane inclination axis
(rotation axis), relative to the normal direction of the film from
-50 degrees up to +50 degrees at intervals of 10 degrees, in 11
points in all with a light having a wavelength of .lamda. nm
applied in the inclined direction; and based on the thus-measured
retardation values, the estimated value of the mean refractive
index and the inputted film thickness value, Rth(.lamda.) of the
film may be calculated by KOBRA 21ADH or WR.
[0045] In the above measurement, as the estimated value of the mean
refractive index, values in Polymer Handbook (by John Wiley &
Sons, Inc.) or those in polymer film catalogues may be used.
Materials of which the mean refractive index is unknown may be
analyzed with an Abbe's refractiometer to determine their data. For
example, the mean refractive index values of some optical films are
as follows:
[0046] cellulose acylate (1.48), cycloolefin polymer (1.52),
polycarbonate (1.59), polymethylmethacrylate (1.49) and polystyrene
(1.59).
[0047] By inputting the value of these average refraction indices
and thickness, KOBRA 21ADH or WR computes nx, ny, nz. From the
computed nx, ny, nz, Nz=(nx-nz)/(nx-ny) is computed further.
[0048] In the invention, "slow axis" of retardation films and
others means the direction in which the refractive index is the
largest. "Visible light region" means from 380 nm to 780 nm. Unless
otherwise specifically indicated, the refractive index is one
measured at .lamda.=589 nm in the visible light region.
[0049] In this specification, the numerical data, the numerical
range and the qualitative expression (for example, "equivalent",
"same", etc.) indicating the optical properties of constitutive
components such as retardation film, liquid crystal layer and
others should be so interpreted as to indicate the numerical data,
the numerical range and the qualitative expression that include the
error range generally acceptable for liquid crystal display devices
and their constitutive components.
1. Cellulose Acylate Film
[0050] The cellulose acylate film of the invention (hereinafter
referred to as a film of the invention) is characterized by
containing a cellulose acylate resin satisfying all the above
formulae (i) to (iii) for the degree of acyl substitution and a
compound of formula (A-1) or formula (B-1). The preferred
embodiment of the film in the invention is descried in detail
hereinunder.
(1-1) Cellulose Acylate Resin
[0051] The film of the invention includes a cellulose acylate resin
satisfying all the above formulae (i) to (iii) for the degree of
acyl substitution. Also, the film of the invention preferably
includes as a main component a cellulose acylate resin satisfying
all the above formulae (i) to (iii) for the degree of acyl
substitution. Here, the term "includes as a main component" means
the cellulose acylate resin when one kind of cellulose acylate
resin is used as a material of the cellulose acylate film, and
means the cellulose acylate resin contained in a highest ratio when
plural kinds of cellulose acylate resins are used as a material of
the film. A cellulose has free hydroxyl groups at 2-position,
3-position and 6-position per a unit of glucose having a .beta.-1,4
bonding. As the material of the cellulose acylate film in the
invention, the cellulose acylate resin that the three hydroxyl
groups are substituted on an acetyl group and a propionyl group
and/or a butyryl group is at least used. Concretely, cellulose
acetate/propionate, cellulose acetate/butylate or cellulose
acetate/propionate/butylate are preferably used.
[0052] The starting cellulose for cellulose acylate includes cotton
linter, wood pulp (hardwood pulp, softwood pulp), etc.; and any
cellulose acylate resin starting from any type of cellulose is
usable herein, and as the case may be, plural types of cellulose
acylate resins may be mixed for use here. The starting cellulose is
described in detail, for example, in Marusawa & Uda's "Plastic
Material Course (17), Cellulose Resin" by Nikkan Kogyo Shinbun
(issued 1970), and Hatsumei Kyokai Disclosure Bulletin No.
2001-1745 (pp. 7-8); and various types of cellulose disclosed in
these are usable here with no specific limitation thereon for use
for the cellulose acylate film in the invention.
[0053] The cellulose acylate film of the invention is characterized
by containing a cellulose acylate satisfying all the following
formulae (i) to (iii):
0.5.ltoreq.A+B.ltoreq.2.7, (i)
0.0.ltoreq.A.ltoreq.2.5, (ii)
0.1.ltoreq.B.ltoreq.2.0. (iii)
[0054] In the formulae (i) to (iii), A means the degree of
substitution with an acetyl group, and B means a total of the
degree of substitution with a propionyl group and the degree of
substitution with a butyryl group.
[0055] When a cellulose acylate resin satisfying the formulae (i)
to (iii) is used, the hydrophilicity of the resin is lowered in
some degree and therefore the resin could easily dissolve in
methylene chloride and alcoholic solvent (including methanol,
ethanol and butanol) that is favorably used as the solvent for
dissolving the cellulose acylate resin, and the film could be
stable in an ordinary humidity condition. Further, the compound
capable of forming a hydrogen bond is more effective. Moreover, the
cellulose acylate resin satisfying the formulae (i) to (iii) can be
produced inexpensively, and its superiority in point of the
production cost in providing optical films for industrial use is
great.
[0056] The cellulose acylate resin also satisfying B.ltoreq.2.0 can
be produced inexpensively, and its superiority in point of the
production cost in providing optical films for industrial
[0057] More preferably, the degree of acyl substitution in the
cellulose acylate resin for the cellulose acylate film of the
invention satisfies all the following formulae (iv) to (vi):
1.0.ltoreq.A+B.ltoreq.2.5, (iv)
0.1.ltoreq.A.ltoreq.2.0, (v)
0.1.ltoreq.B.ltoreq.1.8. (vi)
[0058] In the formulae (iv) to (vi), A means the degree of
substitution with an acetyl group, and B means a total of the
degree of substitution with a propionyl group and the degree of
substitution with a butyryl group.
[0059] Even more preferably, 1.2.ltoreq.A+B.ltoreq.2.5,
0.1.ltoreq.A.ltoreq.1.9, and 0.5.ltoreq.B.ltoreq.1.8.
[0060] The degree of acetyl substitution, the degree of propionyl
substitution and the degree of butyryl substitution in the
cellulose acylate resin each mean the degree of acetylation and the
degree of propionylation and/or butyrylation, respectively, of the
three hydroxyl groups existing in the constitutive unit
(.beta.)-1,4-glycoside bonding glucose) in cellulose. In this
description, the degree of substitution with an acetyl group, a
propionyl group and a butyryl group in the cellulose acylate resin
may be computed by measuring the amount of the bonding fatty acid
per the constitutive unit mass of cellulose. The measurement may be
attained according to "ASTM D817-91".
[0061] Preferably, the cellulose acylate resin has a mass-average
degree of polymerization of from 350 to 800, more preferably a
mass-average degree of polymerization of from 370 to 600. Also
preferably, the cellulose acylate resin for use in the invention
has a number-average molecular weight of from 70000 to 230000, more
preferably a number-average molecular weight of from 75000 to
230000, even more preferably a number-average molecular weight of
from 78000 to 120000.
[0062] The cellulose acylate resin may be produced, using an acid
anhydride or an acid chloride as the acylating agent. A most
popular production method on an industrial scale is as follows:
Cellulose obtained from cotton linter or wood pulp is esterified
with a mixed organic acid component containing an organic acid
(acetic acid, propionic acid, butyric acid) corresponding to the
intended acetyl group and the propionyl group and/or the butyryl
group or its acid anhydride (acetic anhydride, propionic anhydride,
butyric anhydride) thereby producing the intended cellulose acylate
resin.
(1-2) Compound Capable of Forming a Hydrogen Bond
[0063] The compound capable of forming a hydrogen bond used in the
invention satisfies the following conditions (A), (B) and (C):
[0064] (A) the compound has both a hydrogen bond donor moiety and a
hydrogen bond acceptor moiety in the molecule,
[0065] (B) the value obtained by dividing the molecular weight of
the compound by the total of the number of the hydrogen bond donor
moiety and the number of the hydrogen bond acceptor moiety is from
30 to 65, and
[0066] (C) the number of aromatic ring structures is from 1 to
3.
[0067] First, the condition (A) is described.
[0068] Examples of the functional groups that function as the
hydrogen bond donor moiety or the hydrogen bond acceptor moiety in
the compound capable of forming a hydrogen bond used in the
invention are described in for example Table 2 on page 15 of
"Introduction to Hydrogen Bonding" written by Jeffrey, George A.
published by Oxford UP, which is herein incorporated by reference.
In this specification, the total of the number of the hydrogen bond
donor moiety and the number of the hydrogen bond acceptor moiety is
the total number of the functional groups described in the Table
contained in the compound capable of forming a hydrogen bond.
[0069] The compound capable of forming a hydrogen bond used in the
invention has both a hydrogen bond donor moiety and a hydrogen bond
acceptor moiety in the molecule and therefore it forms a strong
hydrogen bond to water whereby it can prevent water from
coordinating the carbonyl group in cellulose acylate. The number of
atoms linking the hydrogen bond donor moiety to the hydrogen bond
acceptor moiety is preferably from 0 to 3, more preferably 1 or 2
from the viewpoint of formation of hydrogen bond to water.
[0070] Nest, the condition (B) is described.
[0071] In the compound capable of forming a hydrogen bond used in
the invention, the value obtained by dividing the molecular weight
of the compound by the total of the number of the hydrogen bond
donor moiety and the number of the hydrogen bond acceptor moiety is
more preferably from 35 to 60. In the case where the value obtained
by dividing the molecular weight of the compound by the total of
the number of the hydrogen bond donor moiety and the number of the
hydrogen bond acceptor moiety is too high, the compound capable of
forming a hydrogen bond is less accessible to the cellulose acylate
to lessen its effect of retarding the fluctuation of retardation
through an environmental change. In the case where the value
obtained by dividing the molecular weight of the compound by the
total of the number of the hydrogen bond donor moiety and the
number of the hydrogen bond acceptor moiety is too low, interaction
among the compounds capable of forming a hydrogen bond is
excessively strong to cause undesirable state where solubility to a
solvent and compatibility to the cellulose acylate are
insufficient.
[0072] Nest, the condition (C) is described.
[0073] The number of aromatic ring structure contained in the
compound capable of forming a hydrogen bond used in the invention
is from 1 to 3. The aromatic ring structure used in the
specification includes heteroaromatic rings as well as aromatic
hydrocarbon rings. A fused ring consisting of two or more fused
aromatic rings counts as one structure. Two aromatic rings bonding
to each other through a linking group count as two structures. For
example, a naphthalene ring having ten carbon atoms counts as one
aromatic structure. In the case where the number of aromatic ring
structure is 4 or more, the size of the molecule of the compound
capable of forming a hydrogen bond is excessively large and thereby
it is less accessible to the carbonyl group in the cellulose
acylate to lessen its effect to retard the fluctuation of optical
properties in humidity change in the environment.
[0074] The compound capable of forming a hydrogen bond used in the
invention preferably has at least one heteroaromatic ring. When the
compound has a heteroaromatic ring, the hetero atom in the
heteroaromatic ring and other acceptor capable of forming a
hydrogen bond or donor capable of forming a hydrogen bond in the
compound capable of forming a hydrogen bond can preferably form a
cyclic hydrogen bond to water easily.
(Hydrophilicity and Hydrophobility of the Compound Capable of
Forming a Hydrogen Bond)
[0075] The hydrophilicity and hydrophobility of the compound
capable of forming a hydrogen bond used in the invention are
preferably controlled within a specific range. In the case where
additives are excessively hydrophobic, the rate of the additives
existing near the cellulose acylate decreases due to insufficient
compatibility to the cellulose acylate. In the case where addtives
are excessively hydrophilic, their solubility to a solvent of the
dope is insufficient.
--C log P Value--
[0076] Octanol-water partition coefficients (log P values) can be
generally measured by the shake flask method described in Japan
Industrial Standards (JIS) Z7260-107 (2000). The octanol-water
partition coefficients (log P values) can be estimated by a
calculative chemical method or experiential method instead of
actual measurement. Known examples of the calculative methods
include Crippen's fragmentation method (J. Chem. Inf. Comput. Sci.,
27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf.
Comput. Sci., 29, 163 (1989)), and Broto's fragmentation method
(Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984)). The Crippen's
fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) is
used in the invention.
[0077] The "C log P value" is a calculated common logarithm (log P)
of an octanol-water partition coefficient P. Known methods and
softwares can be used to calculate the C log P value. In the
invention, the C LOG P program installed in PCModels that is a
system of Daylight Chemical Information Systems is used. When C log
P value of a compound measured by some method differs from C log P
value of the compound calculated by some calculation method, the
Crippen's fragmentation method is used to determine if the compound
is included in the invention.
[0078] The hydrophilicity and hydrophobility of the compound
capable of forming a hydrogen bond can be expressed as an
octanol-water partition coefficient (that may be referred to as log
P hereinafter). The hydrophilicity of the compound capable of
forming a hydrogen bond is characterized by being controlled so
that C log P value of the octanol-water partition coefficient
should be within the range of from 0 to 5.5. The C log P value of
the compound capable of forming a hydrogen bond is preferably from
1.0 to 5.0, more preferably from 2.0 to 4.5.
[0079] The structures of the compound capable of forming a hydrogen
bond are concretely described hereinafter.
[0080] The compound capable of forming a hydrogen bond used in the
invention is preferably represented by the formulae (A-1) to (H-1).
Each structure thereof is described below.
(A) Compound of Formula (A-1)
[0081] First described is the compound of the formula (A-1). In
this specification, the hydrocarbon group such as an alkyl group or
the like may be linear or branched, not contradictory to the scope
of the sprit of the invention.
##STR00015##
[0082] In the formula (A-1), Ra represents an alkyl group, an
alkenyl group, an alkynyl group, a heterocyclic group or an aryl
group; X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each independently
represent a single bond or a divalent linking group; R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 each independently represent a
hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
an aryl group or a heterocyclic group.
[0083] Ra represents an alkyl group, an alkenyl group, an alkynyl
group, a heterocyclic group or an aryl group, and is preferably an
alkyl group or an aryl group.
[0084] When Ra is an alkyl group, preferably, it has from 1 to 20
carbon atoms, more preferably from 3 to 15 carbon atoms, even more
preferably from 6 to 12 carbon atoms.
[0085] When Ra is an alkenyl group, preferably, it has from 2 to 20
carbon atoms, more preferably from 3 to 15 carbon atoms, even more
preferably from 6 to 12 carbon atoms.
[0086] When Ra is an alkynyl group, preferably, it has from 2 to 20
carbon atoms, more preferably from 3 to 15 carbon atoms, even more
preferably from 6 to 12 carbon atoms.
[0087] When Ra is an aryl group, preferably, it has from 6 to 24
carbon atoms, more preferably from 6 to 18 carbon atoms.
[0088] When Ra is a heterocyclic group, preferably, it has from 5
to 23 carbon atoms, more preferably from 5 to 17 carbon atoms.
[0089] Ra may further have a substituent or may have no
substituent. Ra preferably has no substituent from the viewpoint of
improvement of the humidity dependence.
[0090] The following substituent T is exemplified as the
substituent that Ra may have. Examples of the substituent T include
an alkyl group (including, preferably, 1-20 carbon atoms, more
preferably 1-12 carbon atoms, particularly preferably 1-8 carbon
atoms, such as a methyl group, an ethyl group, an isopropyl group,
a tert-butyl group, a n-octyl group, a n-decyl group, a n-hexadecyl
group, a cyclopropyl group, a cyclopentyl group and a cyclohexyl
group), an alkenyl group (including, preferably, 2-20 carbon atoms,
more preferably 2-12 carbon atoms, particularly preferably 2-8
carbon atoms, such as a vinyl group, an allyl group, a 2-butenyl
group and a 3-pentenyl group), an alkynyl group (including,
preferably, 2-20 carbon atoms, more preferably 2-12 carbon atoms,
particularly preferably 2-8 carbon atoms, such as a propagyl group
and a 3-pentynyl group), an aryl group (including, preferably, 6-30
carbon atoms, more preferably 6-20 carbon atoms, particularly
preferably 6-12 carbon atoms, such as a phenyl group, a
p-methylphenyl group and a naphthyl group), amino group (including,
preferably, 0-20 carbon atoms, more preferably 0-10 carbon atoms,
particularly preferably 0-6 carbon atoms, such as an amino group, a
methylamino group, a dimethylamino group, a diethylamino group and
a dibenzylamino group), an alkoxy group (including, preferably,
1-20 carbon atoms, more preferably 1-12 carbon atoms, particularly
preferably 1-8 carbon atoms, such as a methoxy group, an ethoxy
group and a butoxy group), an aryloxy group (including, preferably,
6-20 carbon atoms, more preferably 6-16 carbon atoms, particularly
preferably 6-12 carbon atoms, such as a phenyloxy group and a
2-naphthyloxy group), an acyl group (including, preferably, 1-20
carbon atoms, more preferably 1-16 carbon atoms, particularly
preferably 1-12 carbon atoms, such as an acetyl group, a benzoyl
group, a formyl group and a pivaloyl group), an alkoxycarbonyl
group (including, preferably, 2-20 carbon atoms, more preferably
2-16 carbon atoms, particularly preferably 2-12 carbon atoms, such
as a methoxycarbonyl group and an ethoxycarbonyl group), an
aryloxycarbonyl group (including, preferably, 7-20 carbon atoms,
more preferably 7-16 carbon atoms, and particularly preferably 7-10
carbon atoms, such as a phenyloxycarbonyl group), an acyloxy group
(including, preferably, 2-20 carbon atoms, more preferably 2-16
carbon atoms, particularly preferably 2-10 carbon atoms, such as an
acetoxy group and a benzoyloxy group), an acylamino group
(including, preferably, 2-20 carbon atoms, more preferably 2-16
carbon atoms, particularly preferably 2-10 carbon atoms, such as an
acetylamino group and a benzoylamino group), an alkoxycarbonylamino
group (including, preferably, 2-20 carbon atoms, more preferably
2-16 carbon atoms, particularly preferably 2-12 carbon atoms, such
as a methoxycarbonylamino group), an aryloxycarbonylamino group
(including, preferably, 7-20 carbon atoms, more preferably 7-16
carbon atoms, particularly preferably 7-12 carbon atoms, such as a
phenyloxycarbonylamino group), a sulfonylamino group (including,
preferably, 1-20 carbon atoms, more preferably 1-16 carbon atoms,
particularly preferably 1-12 carbon atoms, such as a
methanesulfonylamino group and a benzenesulfonylamino group), a
sulfamoyl group (including, preferably, 0-20 carbon atoms, more
preferably 0-16 carbon atoms, particularly preferably 0-12 carbon
atoms, such as a sulfamoyl group, a methylsulfamoyl group, a
dimethylsulfamoyl group and a phenylsulfamoyl group), a carbamoyl
group (including, preferably, 1-20 carbon atoms, more preferably
1-16 carbon atoms, particularly preferably 1-12 carbon atoms, such
as a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl
group and a phenylcarbamoyl group), an alkylthio group (including,
preferably, 1-20 carbon atoms, more preferably 1-16 carbon atoms,
particularly preferably 1-12 carbon atoms, such as a methylthio
group and an ethylthio group), an arylthio group (including,
preferably, 6-20 carbon atoms, more preferably 6-16 carbon atoms,
particularly preferably 6-12 carbon atoms, such as a phenylthio
group), a sulfonyl group (including, preferably, 1-20 carbon atoms,
more preferably 1-16 carbon atoms, particularly preferably 1-12
carbon atoms, such as a mesyl group and a tosyl group), a sulfinyl
group (including, preferably, 1-20 carbon atoms, more preferably
1-16 carbon atoms, particularly preferably 1-12 carbon atoms, such
as a methanesulfinyl group and a benzenesulfinyl group), an ureide
group (including, preferably, 1-20 carbon atoms, more preferably
1-16 carbon atoms, and particularly preferably 1-12 carbon atoms,
such as an ureide group, a methylureide group and a phenylureide
group), a phosphoric amide group (including, preferably, 1-20
carbon atoms, more preferably 1-16 carbon atoms, particularly
preferably 1-12 carbon atoms, such as a diethylphosphoric amide
group and a phenylphosphoric amide group), a hydroxyl group, a
mercapto group, a halogen atom (such as a fluorine atom, a chlorine
atom, a bromine atom, an iodine atom and etc.), a cyano group, a
sulfo group, a carboxyl group, a nitro group, a hydroxamic acid
group, a sulfino group, a hydrazino group, an imino group, a
heteroring group (including, preferably, 1-30 carbon atoms, more
preferably 1-12 carbon atoms, wherein examples of the hetero atom
include a nitrogen atom, an oxygen atom and a sulfur atom, and
specific examples include an imidazolyl group, a pyridyl group, a
quinolyl group, a furyl group, a piperidyl group, a morphorino
group, a benzoxysazolyl group, a benzimidazolyl group and a
benzothiazolyl group), and a silyl group (including, preferably,
3-40 carbon atoms, more preferably 3-30 carbon atoms, particularly
preferably 3-24 carbon atoms, such as a trimethylsilyl group and a
triphenylsilyl group). These substituents may further have a
substituent. When there are two substituents or more, they may be
same with or different from each other. Further, when possible,
they may be linked with each other to form a ring.
[0091] X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each independently
represent a single bond or a divalent linking group, and preferably
each is independently a single bond, more preferably all are single
bonds.
[0092] The divalent linking group which X.sup.1, X.sup.2, X.sup.3
and X.sup.4 each independently represent includes, for example, a
divalent linking group represented by the following formula (3), an
alkylene group (preferably having from 1 to 30 carbon atoms, more
preferably from 1 to 3 carbon atoms, even more preferably 2 carbon
atoms), and an arylene group (preferably having from 6 to 30 carbon
atoms, more preferably from 6 to 10 carbon atoms). Of those,
preferred is a divalent linking group represented by the following
formula (P), and more preferred is a carbonyl group.
##STR00016##
[0093] In the formula (P), the side * is the linking site to the N
atom that bonds to the 1,3,5-triazine ring in the compound of the
formula (A-1).
[0094] R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each independently
represent a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, an aryl group or a heterocyclic group, preferably a
hydrogen atom, an alkyl group, an aryl group or a heterocyclic
group, more preferably a hydrogen atom, an alkyl group or a
heterocyclic group, even more preferably a hydrogen atom or an
alkyl group. Preferably, at least one of R.sup.1 or R.sup.2 is a
hydrogen atom; and also preferably at least one of R.sup.3 or
R.sup.4 is a hydrogen atom.
[0095] In the case where R.sup.2, R.sup.3 and R.sup.4 each are an
alkyl group, the group preferably has from 1 to 12 carbon atoms,
more preferably from 1 to 6 carbon atoms, even more preferably from
1 to 4 carbon atoms. From the view point of the humidity dependence
improvability of the compound, preferred are the compounds where
R.sup.1 is an alkyl group, is --C(.dbd.O)--, R.sup.2 is an alkyl
group, X.sup.2 is --C(.dbd.O)--, R.sup.3 is an alkyl group, X.sup.3
is --C(.dbd.O)--, R.sup.4 is an alkyl group, and X.sup.4 is
--C(.dbd.O)--.
[0096] R.sup.1, R.sup.2, R.sup.3 and R.sup.4 can represent an alkyl
group, an alkenyl group, an alkynyl group, an aryl group or a
heterocyclic group, more preferably substituted or unsubstitued
aryl group. Preferred substituents the aryl group may have are the
same as the scope of R.sup.31 to R.sup.34, that is a halogen atom,
a hydroxyl group, a carbamoyl group, sulfamoyl group, an alkyl
group having from 1 to 8 carbon atoms, an alkoxy group having from
1 to 8 carbon atoms, an alkylamino group having from 1 to 8 carbon
atoms and a dialkylamino group having from 1 to 8 carbon atoms.
[0097] In the case where R.sup.2, R.sup.3 and R.sup.4 each are an
alkenyl group, the group preferably has from 2 to 12 carbon atoms,
more preferably from 2 to 6 carbon atoms, even more preferably from
2 to 4 carbon atoms.
[0098] In the case where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each
are an alkynyl group, the group preferably has from 2 to 12 carbon
atoms, more preferably from 2 to 6 carbon atoms, even more
preferably from 2 to 4 carbon atoms.
[0099] In the case where R.sup.2, R.sup.3 and R.sup.4 each are an
aryl group, the group preferably has from 6 to 18 carbon atoms,
more preferably from 6 to 12 carbon atoms, even more preferably 6
carbon atoms from the viewpoint of the humidity dependence
improvability of the compound.
[0100] R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each may have or may
not have an additional substituent, and the substituent includes
the above-mentioned substituent group T.
[0101] The compound of the formula (A-1) is particularly preferably
represented by the following formula (A-2):
##STR00017##
wherein Ra.sup.2 represents an alkyl group, an alkenyl group, an
alkynyl group or an aryl group. The preferred range is the same as
that of Ra described above.
[0102] R.sup.21 and R.sup.24 each independently represent a
hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
an aryl group or a heterocyclic group. The preferred range is the
same as that of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 described
above.
[0103] The compound of the formula (A-1) is particularly preferably
represented by the following formula (A-3):
##STR00018##
wherein Ra.sup.3 represents an alkyl group, an alkenyl group, an
alkynyl group or an aryl group.
[0104] Ra.sup.3 represents an alkyl group, an alkenyl group, an
alkynyl group or an aryl group. The preferred range is the same as
that of Ra described above.
[0105] In the cellulose acylate film of the invention, Ra.sup.3 is
preferably an alkyl group, more preferably unsustituted alkyl group
in order to improve the humidity dependence of retardation while
Rth is reduced.
[0106] The compound of the formula (A-1) is particularly preferably
represented by the following formula (A-4):
##STR00019##
wherein R.sup.31, R.sup.32, R.sup.33 and R.sup.34 each
independently represent a hydrogen atom, a halogen atom, a hydroxyl
group, a carbamoyl group, a sulfamoyl group, an alkyl group having
from 1 to 8 carbon atoms, an alkoxy group having from 1 to 8 carbon
atoms, an alkylamino group having from 1 to 8 carbon atoms, a
dialkylamino group having from 1 to 8 carbon atoms. R.sup.4
represents an alkyl group, an alkenyl group, an alkynyl group or an
aryl group. The preferred range is the same as that of Ra described
above.
(B) Compound of Formula (B-1)
[0107] Next described is the compound of the formula (B-1).
##STR00020##
wherein Rb and Rc each independently represent an alkyl group, an
alkenyl group, an alkynyl group, a heterocyclic group or an aryl
group; X.sup.5 and X.sup.6 each independently represent a single
bond or a divalent linking group; R.sup.5 and R.sup.6 each
independently represent a hydrogen atom, an alkyl group, an alkenyl
group, an alkynyl group, an aryl group or a heterocyclic group.
[0108] Rb and Rc each independently represent an alkyl group, an
alkenyl group, an alkynyl group, a heterocyclic group or an aryl
group. The preferred range is the same as that of Ra described
above.
[0109] X.sup.5 and X.sup.6 each independently represent a single
bond or a divalent linking group. The preferred range is the same
as that of X.sup.1, X.sup.2, X.sup.3 and X.sup.4 described
above.
[0110] R.sup.5 and R.sup.6 each independently represent a hydrogen
atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl
group or a heterocyclic group. The preferred range is the same as
that of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 described above.
[0111] The compound of the formula (B-1) is particularly preferably
represented by the following formula (B-2):
##STR00021##
wherein Rb.sup.2 and Rc.sup.2 each independently represent an alkyl
group, an alkenyl group, an alkynyl group or an aryl group. The
preferred range is the same as that of Ra described above.
[0112] R.sup.25 represents a hydrogen atom, an alkyl group, an
alkenyl group, an alkynyl group, an aryl group or a heterocyclic
group. The preferred range is the same as that of R.sup.21 and
R.sup.24 described above.
[0113] The compound of the formula (B-1) is particularly preferably
represented by the following formula (B-3):
##STR00022##
wherein Rb.sup.3 and Rc.sup.3 each independently represent an alkyl
group, an alkenyl group, an alkynyl group or an aryl group. The
preferred range is the same as that of Ra described above.
[0114] The compound of the formula (B-1) is particularly preferably
represented by the following formula (B-4):
##STR00023##
wherein Rb.sup.4 and Rc.sup.4 each independently represent an alkyl
group, an alkenyl group, an alkynyl group or an aryl group.
[0115] In the cellulose acylate film of the invention, Rb.sup.3 and
Rc.sup.3 are preferably an alkyl group, more preferably
unsustituted alkyl group in order to improve the humidity
dependence of retardation while Rth is reduced. From the same
viewpoint, Rb.sup.4 and Rc.sup.4 are preferably an alkyl group.
[0116] R.sup.41 and R.sup.42 each independently represent a
hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
an aryl group or a heterocyclic group. The preferred range is the
same as that of R.sup.21 and R.sup.24 described above.
[0117] Specific examples of the compounds of the formula (A-1) or
(B-1) are mentioned below, to which, however, the invention should
not be limited.
##STR00024## ##STR00025## ##STR00026## ##STR00027##
(Production Method for Compound of Formula (A-1) or (B-1))
[0118] The production method for the compound of the formula (A-1)
or (B-1) to be contained in the compound capable of forming a
hydrogen bond is not specifically defined; and the compound may be
produced according to a known method. Preferred production method
which can be used in the invention are for example a method of
heating dicyanodiamide and a nitrile compound in an alcohol in the
presence of an inorganic base such as potassium hydroxide to form a
triazine ring as descried in U.S. Pat. No. 3,478,026 and Chem. Eur.
J. 2005, 11, 6616-6628; a method of subjecting cyanuric chloride as
a raw material to a substitution reaction with a Grignard reagent
and then an amine compound as described in Tetrahedron 2000, 56,
9705-9711; and a method of reacting an imidoyl guanidine with a
carboxylic chloride or an ester to give a
monoamino-di-substituted-s-triazine compound as described in
Journal of Synthetic Organic Chemistry, 1967, vol. 25 (11),
1048-1051.
[0119] The compounds of the formula (A-1) or (B-1) may be
commercially available.
(C) Compound of Formula (C-1)
[0120] Next described is the compound of the formula (C-1).
##STR00028##
wherein Ra.sup.11 represents an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group; Rb.sup.11,
Rc.sup.11, Rd.sup.11 and Re.sup.11 each independently represent a
hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
a heterocyclic group or an aryl group; Q.sup.1 represents --O--,
--S-- or --NRf--; Rf represents a hydrogen atom, an alkyl group, an
alkenyl group, an alkynyl group, a heterocyclic group or an aryl
group, and may be taken together with Ra.sup.11 to form a ring;
X.sup.11, X.sup.12 and X.sup.13 each independently represent a
single bond or a divalent linking group; and X.sup.14 represents
any one selected from the group of divalent linking groups of the
formula (P) described above.
[0121] The compound of the formula (C-1) is particularly preferably
represented by the following formula (C-2):
##STR00029##
wherein Ra.sup.12 represents an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group; Rb.sup.12 and
Rd.sup.12 each independently represent a hydrogen atom, an alkyl
group, an alkenyl group, an alkynyl group, a heterocyclic group or
an aryl group; Q.sup.2 represents --O--, --S-- or --NRf--; Rf
represents a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group, and may be
taken together with Ra.sup.12 to form a ring; X.sup.11, X.sup.12
and X.sup.13 each independently represent a single bond or a
divalent linking group; and X.sup.14 represents any one selected
from the group of divalent linking groups of the formula (P)
described above.
[0122] The compound of the formula (C-1) is particularly preferably
represented by the following formula (C-3):
##STR00030##
wherein Ra.sup.13 represents an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group; and Q.sup.3
represents --O--, --S-- or --NRf--; Rf represents a hydrogen atom,
an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group, and may be taken together with Ra.sup.13 to
form a ring.
[0123] The compound of the formula (C-1) is particularly preferably
represented by the following formula (C-4):
##STR00031##
wherein R.sup.41, R.sup.42, R.sup.43 and R.sup.44 each
independently represent a hydrogen atom, a halogen atom, a hydroxyl
group, a carbamoyl group, a sulfamoyl group, an alkyl group having
from 1 to 8 carbon atoms, an alkoxy group having from 1 to 8 carbon
atoms, an alkylamino group having from 1 to 8 carbon atoms, a
dialkylamino group having from 1 to 8 carbon atoms; R.sup.14
represents an alkyl group, an alkenyl group, an alkynyl group or an
aryl group; Q.sup.4 represents --O--, --S-- or --NRf--; and Rf
represents a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group, and may be
taken together with Ra.sup.14 to form a ring.
(D) Compound of Formula (D-1)
[0124] Next described is the compound of the formula (D-1).
##STR00032##
wherein Ra.sup.21 and Ra.sup.21 each independently represent an
alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group; Rd.sup.21 and Re.sup.21 each independently
represent a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group; Q.sup.11
represents --O--, --S-- or --NRf--; Rf represents a hydrogen atom,
an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group, and may be taken together with Ra.sup.21 to
form a ring; Q.sup.12 represents --O--, --S-- or --NRh--; Rh
represents a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group, and may be
taken together with Rg.sup.21 to form a ring; X.sup.23 represents a
single bond or a divalent linking group; and X.sup.24 represents
anyone selected from the group of divalent linking groups of the
formula (P) described above.
[0125] The compound of the formula (D-1) is particularly preferably
represented by the following formula (D-2):
##STR00033##
wherein Ra.sup.22 and Rg.sup.22 each independently represent an
alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group; Rd.sup.22 represents a hydrogen atom, an
alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group; Q.sup.13 represents --O--, --S-- or
--NRf--; Rf represents a hydrogen atom, an alkyl group, an alkenyl
group, an alkynyl group, a heterocyclic group or an aryl group, and
may be taken together with Ra.sup.22 to form a ring; Q.sup.14
represents --O--, --S-- or --NRh--; Rh represents a hydrogen atom,
an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group, and may be taken together with Rg.sup.22 to
form a ring; and X.sup.25 represents any one selected from the
group of divalent linking groups of the formula (P) described
above.
[0126] The compound of the formula (D-1) is particularly preferably
represented by the following formula (D-3):
##STR00034##
wherein Ra.sup.23 and Rg.sup.23 each independently represent an
alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group; Q.sup.15 represents --O--, --S-- or
--NRf--; Rf represents a hydrogen atom, an alkyl group, an alkenyl
group, an alkynyl group, a heterocyclic group or an aryl group, and
may be taken together with Ra.sup.23 to form a ring; Q.sup.16
represents --O--, --S-- or --NRh--; and Rh represents a hydrogen
atom, an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group, and may be taken together with
Rg.sup.23 to form a ring.
[0127] The compound of the formula (D-1) is particularly preferably
represented by the following formula (D-4):
##STR00035##
wherein Ra.sup.51 and Rg.sup.52 each independently represent a
hydrogen atom, a halogen atom, a hydroxyl group, a carbamoyl group,
a sulfamoyl group, an alkyl group having from 1 to 8 carbon atoms,
an alkoxy group having from 1 to 8 carbon atoms, an alkylamino
group having from 1 to 8 carbon atoms, a dialkylamino group having
from 1 to 8 carbon atoms; Ra.sup.24 and Rg.sup.24 each
independently represent an alkyl group, an alkenyl group, an
alkynyl group or an aryl group; Q.sup.17 represents --O--, --S-- or
--NRf--; and Rf represents a hydrogen atom, an alkyl group, an
alkenyl group, an alkynyl group, a heterocyclic group or an aryl
group, and may be taken together with Ra.sup.24 to form a ring;
Q.sup.18 represents --O--, --S-- or --NRh--; and Rh represents a
hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group
or an aryl group, and may be taken together with Rg.sup.24 to form
a ring.
[0128] Specific examples of the compounds of the formula (C-1) or
(D-1) are mentioned below, to which, however, the invention should
not be limited.
##STR00036##
TABLE-US-00001 Compound R1 R2 R3 C-101 C-102 C-103 C-104 C-105
C-106 C-107 C-108 C-109 C-110 ##STR00037## H o-Me m-Me p-Me o-OMe
m-OMe p-OMe p-t-Bu m-Cl m-F H o-Me m-Me p-Me o-OMe m-OMe p-OMe
p-t-Bu m-Cl m-F C-111 C-112 C-113 C-114 C-115 C-116 C-117 C-118
C-119 C-120 ##STR00038## H o-Me m-Me p-Me o-OMe m-OMe p-OMe p-t-Bu
m-Cl m-F H o-Me m-Me p-Me o-OMe m-OMe p-OMe p-t-Bu m-Cl m-F C-121
C-122 C-123 C-124 C-125 C-126 C-127 C-128 C-129 C-130 ##STR00039##
H o-Me m-Me p-Me o-OMe m-OMe p-OMe p-t-Bu m-Cl m-F H o-Me m-Me p-Me
o-OMe m-OMe p-OMe p-t-Bu m-Cl m-F C-131 C-132 C-133 C-134 C-135
C-136 C-137 C-138 C-139 C-140 ##STR00040## H o-Me m-Me p-Me o-OMe
m-OMe p-OMe p-t-Bu m-Cl m-F H o-Me m-Me p-Me o-OMe m-OMe p-OMe
p-t-Bu m-Cl m-F C-141 H.sub.2N--* H H C-142 o-Me o-Me C-143 m-Me
m-Me C-144 p-Me p-Me C-145 o-OMe o-OMe C-146 m-OMe m-OMe C-147
p-OMe p-OMe C-148 p-t-Bu p-t-Bu C-149 m-Cl m-Cl C-150 m-F m-F C-151
C-152 C-153 C-154 C-155 C-156 C-157 C-158 C-159 C-160 ##STR00041##
H o-Me m-Me p-Me o-OMe m-OMe p-OMe p-t-Bu m-Cl m-F H o-Me m-Me p-Me
o-OMe m-OMe p-OMe p-t-Bu m-Cl m-F C-161 C-162 C-163 C-164 C-165
C-166 C-167 C-168 C-169 C-170 ##STR00042## H o-Me m-Me p-Me o-OMe
m-OMe p-OMe p-t-Bu m-Cl m-F H o-Me m-Me p-Me o-OMe m-OMe p-OMe
p-t-Bu m-Cl m-F C-171 C-172 C-173 C-174 C-175 C-176 C-177 C-178
C-179 C-180 ##STR00043## H o-Me m-Me p-Me o-OMe m-OMe p-OMe p-t-Bu
m-Cl m-F H o-Me m-Me p-Me o-OMe m-OMe p-OMe p-t-Bu m-Cl m-F
##STR00044##
TABLE-US-00002 Compound R2 R3 C-181 H H C-182 o-Me o-Me C-183 m-Me
m-Me C-184 p-Me p-Me C-185 o-OMe o-OMe C-186 m-OMe m-OMe C-187
p-OMe p-OMe C-188 p-t-Bu p-t-Bu C-189 m-Cl m-Cl C-190 m-F m-F
##STR00045##
TABLE-US-00003 Compound R3 D-101 H D-102 o-Me D-103 m-Me D-104 p-Me
D-105 o-OMe D-106 m-OMe D-107 p-OMe D-108 p-t-Bu D-109 m-Cl D-110
m-F
(E) Compound of Formula (E-1)
[0129] Next described is the compound of the formula (E-1).
##STR00046##
wherein Y.sup.1 represents a methine group or --N--; Ra.sup.31
represents an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group; Rb.sup.31, Rc.sup.31,
Rd.sup.31 and Re.sup.31 each independently represent a hydrogen
atom, an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group; Q.sup.21 represents a single
bond, --O--, --S-- or --NRf--; Rf represents a hydrogen atom, an
alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group, and may be taken together with Ra.sup.31 to
form a ring; X.sup.31, X.sup.32 and X.sup.33 each independently
represent a single bond or a divalent linking group; and X.sup.34
represents any one selected from the group of divalent linking
groups of the following formula (Q):
##STR00047##
wherein the side * is the linking site to the N atom that bonds to
the heterocyclic ring in the compound of the formula (E-1).
[0130] The compound of the formula (E-1) is particularly preferably
represented by the following formula (E-2):
##STR00048##
wherein Y.sup.2 represents a methine group or --N--; Ra.sup.32
represents an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group; Rb.sup.32, Rc.sup.32 and
Rd.sup.32 each independently represent a hydrogen atom, an alkyl
group, an alkenyl group, an alkynyl group, a heterocyclic group or
an aryl group; Q.sup.22 represents a single bond, --O--, --S-- or
--NRf--; Rf represents a hydrogen atom, an alkyl group, an alkenyl
group, an alkynyl group, a heterocyclic group or an aryl group, and
may be taken together with Ra.sup.32 to form a ring; X.sup.35
represents a single bond or a divalent linking group; and X.sup.36
represents a single bond or any one selected from the group of
divalent linking groups of the formula (Q) described above.
[0131] The compound of the formula (E-1) is particularly preferably
represented by the following formula (E-3):
##STR00049##
wherein Y.sup.3 represents a methine group or --N--; Ra.sup.33
represents an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group; and Q.sup.23 represents a
single bond, --O--, --S-- or --NRf--; Rf represents a hydrogen
atom, an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group, and may be taken together with
Ra.sup.33 to form a ring.
[0132] The compound of the formula (E-1) is particularly preferably
represented by the following formula (E-4):
##STR00050##
wherein Y.sup.4 represents a methine group or --N--; Ra.sup.34
represents an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group; Q.sup.24 represents a single
bond, --O--, --S-- or --NRf--; Rf represents a hydrogen atom, an
alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group, and may be taken together with Ra.sup.34 to
form a ring; and Ra.sup.61, Ra.sup.62, Ra.sup.63 and Ra.sup.64 each
independently represent a hydrogen atom, a halogen atom, a hydroxyl
group, a carbamoyl group, a sulfamoyl group, an alkyl group having
from 1 to 8 carbon atoms, an alkoxy group having from 1 to 8 carbon
atoms, an alkylamino group having from 1 to 8 carbon atoms, a
dialkylamino group having from 1 to 8 carbon atoms.
[0133] The compound of the formula (E-1) is particularly preferably
represented by the following formula (E-5):
##STR00051##
wherein R.sup.65, R.sup.66, R.sup.67 and R.sup.68 each
independently represent a hydrogen atom, a halogen atom, a hydroxyl
group, a carbamoyl group, a sulfamoyl group, an alkyl group having
from 1 to 8 carbon atoms, an alkoxy group having from 1 to 8 carbon
atoms, an alkylamino group having from 1 to 8 carbon atoms, a
dialkylamino group having from 1 to 8 carbon atoms; Ra.sup.35
represents an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group; Q.sup.25 represents a single
bond, --O--, --S-- or --NRf--; and Rf represents a hydrogen atom,
an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group, and may be taken together with Ra.sup.35 to
form a ring.
(F) Compound of Formula (F-1)
[0134] Next described is the compound of the formula (F-1).
##STR00052##
wherein Y.sup.11 represents a methine group or --N--; Ra.sup.41 and
Rg.sup.41 each independently represent an alkyl group, an alkenyl
group, an alkynyl group, a heterocyclic group or an aryl group;
Rd.sup.41 and Re.sup.41 each independently represent a hydrogen
atom, an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group; Q.sup.31 represents --O--,
--S-- or --NRf--; Rf represents a hydrogen atom, an alkyl group, an
alkenyl group, an alkynyl group, a heterocyclic group or an aryl
group, and may be taken together with Ra.sup.41 to form a ring;
Q.sup.32 represents --O--, --S-- or --NRh--; Rh represents a
hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
a heterocyclic group or an aryl group, and may be taken together
with Rg.sup.41 to form a ring; X.sup.43 represents a single bond or
a divalent linking group; and X.sup.44 represents any one selected
from the group of divalent linking groups of the formula (P)
described above wherein the side * is the linking site to the N
atom that bonds to the heterocyclic ring in the compound of the
formula (F-1).
[0135] The compound of the formula (F-1) is particularly preferably
represented by the following formula (F-2):
##STR00053##
wherein Y.sup.12 represents a methine group or --N--; Ra.sup.42 and
Rg.sup.42 each independently represent an alkyl group, an alkenyl
group, an alkynyl group, a heterocyclic group or an aryl group;
Rd.sup.42 represents a hydrogen atom, an alkyl group, an alkenyl
group, an alkynyl group, a heterocyclic group or an aryl group;
Q.sup.33 represents --O--, --S-- or --NRf--; Rf represents a
hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
a heterocyclic group or an aryl group, and may be taken together
with Ra.sup.42 to form a ring; Q.sup.34 represents --O--, --S-- or
--NRh--; Rh represents a hydrogen atom, an alkyl group, an alkenyl
group, an alkynyl group, a heterocyclic group or an aryl group, and
may be taken together with Rg.sup.42 to form a ring; X.sup.43
represents a single bond or a divalent linking group; and X.sup.45
represents any one selected from the group of divalent linking
groups of the formula (P) described above wherein the side * is the
linking site to the N atom that bonds to the heterocyclic ring in
the compound of the formula (F-2).
[0136] The compound of the formula (F-1) is particularly preferably
represented by the following formula (F-3):
##STR00054##
wherein Y.sup.13 represents a methine group or --N--; Ra.sup.43 and
Rg.sup.43 each independently represent an alkyl group, an alkenyl
group, an alkynyl group, a heterocyclic group or an aryl group;
Q.sup.35 represents --O--, --S-- or --NRf--; Rf represents a
hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
a heterocyclic group or an aryl group, and may be taken together
with Ra.sup.43 to form a ring; Q.sup.36 represents --O--, --S-- or
--NRh--; and Rh represents a hydrogen atom, an alkyl group, an
alkenyl group, an alkynyl group, a heterocyclic group or an aryl
group, and may be taken together with Rg.sup.43 to form a ring.
[0137] The compound of the formula (F-1) is particularly preferably
represented by the following formula (F-4):
##STR00055##
wherein Y.sup.14 represents a methine group or --N--; Ra.sup.44 and
Rg.sup.44 each independently represent an alkyl group, an alkenyl
group, an alkynyl group, a heterocyclic group or an aryl group;
Q.sup.37 represents a single bond, --O--, --S-- or --NRf--; Rf
represents a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group, and may be
taken together with Ra.sup.44 to form a ring; Q.sup.38 represents a
single bond, --O--, --S-- or --NRf--; Rf represents a hydrogen
atom, an alkyl group, an alkenyl group, an alkynyl group, a
heterocyclic group or an aryl group, and may be taken together with
Rg.sup.44 to form a ring; and R.sup.71 and R.sup.72 each
independently represent a hydrogen atom, a halogen atom, a hydroxyl
group, a carbamoyl group, a sulfamoyl group, an alkyl group having
from 1 to 8 carbon atoms, an alkoxy group having from 1 to 8 carbon
atoms, an alkylamino group having from 1 to 8 carbon atoms, a
dialkylamino group having from 1 to 8 carbon atoms.
[0138] The compound of the formula (F-1) is particularly preferably
represented by the following formula (F-5):
##STR00056##
wherein Ra.sup.45 and Rg.sup.45 each independently represent an
alkyl group, an alkenyl group, an alkynyl group, a heterocyclic
group or an aryl group; Q.sup.39 represents a single bond, --O--,
--S-- or --NRf--; Rf represents a hydrogen atom, an alkyl group, an
alkenyl group, an alkynyl group, a heterocyclic group or an aryl
group, and may be taken together with Ra.sup.45 to form a ring;
Q.sup.40 represents a single bond, --O--, --S-- or --NRf--; Rf
represents a hydrogen atom, an alkyl group, an alkenyl group, an
alkynyl group, a heterocyclic group or an aryl group, and may be
taken together with Rg.sup.45 to form a ring; and R.sup.73 and
R.sup.74 each independently represent a hydrogen atom, a halogen
atom, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an
alkyl group having from 1 to 8 carbon atoms, an alkoxy group having
from 1 to 8 carbon atoms, an alkylamino group having from 1 to 8
carbon atoms, a dialkylamino group having from 1 to 8 carbon
atoms.
[0139] Specific examples of the compounds of the formula (E-1) or
(F-1) are mentioned below, to which, however, the invention should
not be limited.
##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061##
##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066##
##STR00067## ##STR00068## ##STR00069## ##STR00070##
##STR00071##
[0140] The compound of the formula (E-1) can be synthesized by for
example the method of the scheme 1 below. That is, the compound of
the formula (E-1) can be synthesized by the reaction of a compound
of the formula (E-1a) with a compound of the formula (E-1b) in the
presence of a base in an organic solvent. Commercially available
products and materials synthesized by known synthetic methods can
be used as the compound of the formula (E-1a) and the compound of
the formula (E-1b). Examples of the organic solvent used in the
reaction include an alcohol (for example methanol and ethanol), an
ester (for example ethyl acetate), a hydrocarbon (for example
toluene), an ether (for example tetrahydrofuran), an amide (for
example dimethylformamide, demethylacetoamide, N-methylpyrrolidone,
N-ethylpyrrolidone), a halogenated hydrocarbon (for example
dichloromethane), a nitrile (for example acetonitrile), and a mixed
solvent thereof. Preferred are an alcohol and an amide and
particularly preferred are methanol, ethanol, N-methylpyrrolidone
and N-ethylpyrrolidone. A mixed solution of methanol, ethanol,
N-methylpyrrolidone and N-ethylpyrrolidone is also particularly
preferred.
[0141] As the base, any of an inorganic base (for example potassium
carbonate) and an organic base (for example triethylamine, sodium
methoxide and sodium ethoxide) can be used. An organic base is
preferred and sodium ethoxide is particularly preferred. The base
is preferably used in an amount of from 0.5 to 10 equivalents,
particularly preferably from 1 to 3 equivalents relative to the
content of the compound of the formula (E-1b).
[0142] The reaction temperature is generally from -20.degree. C. to
the boiling point of the solvent used in the reaction, preferably
from a room temperature to the boiling point of the solvent. The
reaction time is generally from 10 minutes to 3 days, preferably
from 1 hour to 1 day. The reaction can be conducted in a nitrogen
atmosphere or under a reduced pressure. Particularly, in the case
where the leaving group Z is an alkoxy group or an aryl group, the
reaction under a reduced pressure is also preferable.
##STR00072##
wherein Z represents a leaving group, preferably a halogen atom, an
alkoxy group or an aryloxy group.
[0143] The compound of the formula (E-2) used in the invention can
be synthesized by the method of the scheme 2 below. That is, the
compound of the formula (E-2) can be synthesized by the reaction of
a compound of the formula (E-2a), a compound of the formula (E-2b)
and a compound of the formula (E-2c) in the presence of a base in
an organic solvent. Commercially available products and materials
synthesized by known synthetic methods can be used as the compound
of the formula (E-2a), the compound of the formula (E-2b) and a
compound of the formula (E-2c). Preferable examples of the organic
solvent used in the reaction are the same as above. Preferable
examples of the base used in the reaction are the same as above.
The base is preferably used in an amount of from 0.5 to 10
equivalents, particularly preferably from 1 to 3 equivalents
relative to the total content of the compound of the formula (E-2b)
and the compound of the formula (E-2c). Preferable reaction
temperature and preferable reaction time are the same as above.
##STR00073##
(G) Compound of Formula (G-1)
[0144] Next described is the compound of the formula (G-1).
##STR00074##
wherein L.sup.1 represents a single bond or a divalent linking
group having a hetero atom, preferably a divalent linking group
having a hetero atom. The divalent linking group having a hetero
atom represented by L.sup.1 is preferably a linking group in which
a single atom has the two bond for linkage of the group. Examples
of such linking group include --O--, --N(R.sup.82)--,
--C(.dbd.O)--, --S--, --S(.dbd.O).sub.2 and a combination thereof.
The definition of R.sup.82 is the same as R.sup.3 described above.
R.sup.82 is preferably a hydrogen atom, an alkyl group having from
1 to 15 carbon atoms (more preferably from 1 to 10 carbon atoms,
particularly preferably from 1 to 5 carbon atoms, more particularly
preferably a methyl group).
[0145] Among them, a linking group consisting of --O--, --NH--,
--N(CH.sub.3)--, --C(.dbd.O)-- and a combination thereof are
preferable, and --O--, --NH--C(.dbd.O)-- and --N(CH.sub.3)-- are
more preferable.
[0146] R.sup.81 in the formula (C-1) represents a hydrogen atom, an
alkyl group having from 1 to 20 carbon atoms, an alkenyl group
having from 2 to 20 carbon atoms, an alkynyl group having from 2 to
20 carbon atoms, a heteroaryl group having from 5 to 20 carbon
atoms or an aryl group having from 6 to 20 carbon atoms.
[0147] When R.sup.81 is an alkyl group, preferably, it has from 1
to 15 carbon atoms, more preferably from 1 to 10 carbon atoms, even
more preferably from 1 to 5 carbon atoms.
[0148] When R.sup.81 is an alkenyl group, preferably, it has from 2
to 15 carbon atoms, more preferably from 2 to 10 carbon atoms, even
more preferably from 2 to 5 carbon atoms.
[0149] When R.sup.81 is an alkynyl group, preferably, it has from 2
to 15 carbon atoms, more preferably from 2 to 10 carbon atoms, even
more preferably from 2 to 5 carbon atoms.
[0150] When R.sup.81 is an alkyl group, an alkenyl group or an
alkynyl group, it may be cyclic, linear or branched, preferably
linear or branched, more preferably linear.
[0151] When R.sup.81 is a heteroaryl group, preferably, it has from
5 to 18 carbon atoms, more preferably from 5 to 12 carbon
atoms.
[0152] When R.sup.81 is an aryl group, preferably, it has from 6 to
18 carbon atoms, more preferably from 6 to 12 carbon atoms.
[0153] When R.sup.81 is an arylalkyl group, preferably, it has from
7 to 18 carbon atoms, more preferably from 7 to 12 carbon
atoms.
[0154] R.sup.81 may have a substituent or may be unsubstituted.
Substituents are not particularly limited so long as the gist of
the invention is not deteriorated. Preferable substituents are a
halogen atom, an alkyl group having from 1 to 20 darbon atoms, an
alkenyl group having from 1 to 20 carbon atoms, an alkynyl group
having from 2 to 20 carbon atoms, a heteroaryl group having from 5
to 20 carbon atoms, and an aryl group having from 6 or 20 carbon
atoms. More preferable substituent is an aryl group having from 6
or 20 carbon atoms. Particularly in the case where R.sup.81 is a
substituted alkyl group, the substituent is preferably a phenyl
group.
[0155] Preferable combinations of L.sup.1 and R.sup.81 are as
follows.
[0156] In the case where L.sup.1 is --O--, R.sup.81 is an alkyl
group having from 1 to 15 carbon atoms or an arylalkyl group, more
preferably an arylalkyl group.
[0157] In the case where L.sup.1 is --NH--, R.sup.81 is an alkyl
group having from 1 to 15 carbon atoms or an arylalkyl group, more
preferably an arylalkyl group.
[0158] In the case where L.sup.1 is --NH--C(.dbd.O)--, R.sup.81 is
an alkyl group having from 1 to 15 carbon atoms or an aryl group,
more preferably an alkyl group.
[0159] In the case where L.sup.1 is --N(CH.sub.3)--, R.sup.81 is an
alkyl group having from 1 to 15 carbon atoms or an alkyl group,
more preferably an alkyl group.
[0160] From the viewpoint of retard the fluctuation of retardation
in humidity change in the environment, R.sup.81 is preferably a
hydrogen atom or an alkyl group having from 1 to 20 carbon
atoms.
[0161] Among the compounds of the formula (G-1), the compound of
capable of forming a hydrogen bond is preferably a compound in
which the number of amino group in purine base skeleton
(substituents are uncounted) is preferably 0 or 1.
[0162] The compound of capable of forming a hydrogen bond is
preferably a compound of the formula (G-1) in which R.sup.81 is not
a hydrogen atom. That is, the compound of capable of forming a
hydrogen bond having the nucleic acid base skeleton is preferably
represented by the following formula (G-2).
##STR00075##
wherein L.sup.2 represents a single bond or a divalent linking
group having a hetero atom; and R.sup.82 represents a hydrogen
atom, an alkyl group having from 1 to 20 carbon atoms, an alkenyl
group having from 2 to 20 carbon atoms, an alkynyl group having
from 2 to 20 carbon atoms, an aryl group having from 6 to 20 carbon
atoms or an arylalkyl group having from 7 to 20 carbon atoms.
[0163] The preferable range of L.sup.2 in the formula (G-2) is the
same as that of L.sup.1 in the formula (G-1).
[0164] R.sup.82 represents a hydrogen atom, an alkyl group having
from 1 to 20 carbon atoms, an alkenyl group having from 2 to 20
carbon atoms, an alkynyl group having from 2 to 20 carbon atoms, an
aryl group having from 6 to 20 carbon atoms or an arylalkyl group
having from 7 to 20 carbon atoms. The preferable number of the
carbon atom in each group is the same as that in R.sup.81.
[0165] R.sup.82 is more preferably a methyl group, a phenyl group
or a benzyl group.
[0166] Preferable combinations of L.sup.2 and R.sup.82 are the same
as those of L.sup.1 and R.sup.81 in the formula (G-1).
[0167] The compound capable of forming a hydrogen bond preferably
control the interaction between the compound having a nucleic acid
base skeleton and cellulose acylate to prevent generation of haze
in the cellulose acylate film and prevent breeding out and
evaporation from the film.
[0168] Preferable structural moieties of the compound having a
nucleic acid base skeleton which can interact with cellulose
acylate through a hydrogen bond or others are a purine base
skeleton, an ether bond structure, an ester bond structure, an
amido bond structure, --NH-- linking group structure, etc.
[0169] Specific examples of the compounds of the formula (G-1)
having a nucleic acid base skeleton are mentioned below, to which,
however, the compounds of the formula (G-1) having a nucleic acid
base skeleton which can be used as the compound capable of forming
a hydrogen bond should not be limited.
##STR00076## ##STR00077## ##STR00078## ##STR00079##
(H) Compound of Formula (H-1)
[0170] Next described is the compound of the formula (H-1).
##STR00080##
wherein L.sup.3 represents a single bond or a divalent linking
group having a hetero atom; and R.sup.85 represents an alkyl group
having from 1 to 20 carbon atoms, an alkenyl group having from 2 to
20 carbon atoms, an alkynyl group having from 2 to 20 carbon atoms,
an aryl group having from 6 to 20 carbon atoms or an arylalkyl
group having from 7 to 20 carbon atoms; R.sup.83 and R.sup.84 each
independently represent a hydrogen atom, an alkyl group, an alkenyl
group, an alkynyl group, a heterocyclic group or an aryl group; and
X.sup.53 and X.sup.54 each independently represent any one selected
from the group of divalent linking groups of the following formula
(P) described above wherein the side * is the linking site to the N
atom that bonds to the heterocyclic ring in the compound of the
formula (H-1).
[0171] Preferable examples of the compounds of the formula (H-1)
are mentioned below.
##STR00081## ##STR00082##
(Physical Properties)
[0172] Preferably, the compounds of the formulae (A-1) to (H-1)
have a molecular weight of from 100 to 1000, more preferably from
150 to 700, most preferably from 150 to 450.
(Amount to be Added)
[0173] The amount of the compounds of the formulae (A-1) to (H-1)
to be added to the film of the invention is preferably at most 30
parts by mass relative to 100 parts by mass of the cellulose
acylate resin therein, more preferably from 1 to 30 parts by mass,
even more preferably from 2 to 20 parts by mass, still more
preferably from 3 to 15 parts by mass.
[0174] Also preferably, the total content of the compound capable
of forming a hydrogen bond in the film of the invention is at most
35 parts by mass relative to 100 parts by mass of the cellulose
acylate resin therein, more preferably at most 30 parts by mass,
even more preferably at most 20 parts by mass. The compound capable
of forming a hydrogen bond is not limited to the compounds of the
formulae (A-1) to (H-1).
(1-3) Other Additives:
[0175] The cellulose acylate film of the invention may contain any
other additive than the compounds of the formulae (A-1) to (H-1)
for various purposes. When the cellulose acylate film is produced
according to a solvent-casting method, the additive may be added to
a cellulose acylate dope. The timing of addition is not
specifically defined. The additive is selected from those miscible
with cellulose acylate, and soluble in a cellulose acylate dope in
a solvent-casting method. The additive is added for the purpose of
regulating the optical properties of the cellulose acylate film and
for regulating other properties thereof.
(Plasticizer)
[0176] The cellulose acylate film of the invention preferably
contains a plasticizer for enhancing the film formability thereof.
As the plasticizer, preferred are saccharide-type plasticizers
selected from a group of compounds of saccharides and their
derivatives, or oligomer-type plasticizers selected from oligomers
of polycondensate esters of dicarboxylic acids and dials and their
derivatives, as enhancing the environmental humidity resistance of
the cellulose acylate film. Concretely, the plasticizer of the type
can reduce humidity-dependent Rth fluctuation of film. When both
such a saccharide-type plasticizer and an oligomer-type plasticizer
are used simultaneously, the effect thereof for reducing the
humidity-dependent Rth fluctuation of film could be high.
(Saccharide-Type Plasticizer)
[0177] As described in the above, the cellulose acylate film of the
invention preferably contains at least one compound selected from a
group consisting of saccharides and their derivatives. Above all,
compounds selected from a group of monomeric to 10-meric
saccharides and their derivatives are especially preferred for the
plasticizer. Their examples include saccharide derivatives in which
a part or all of the hydrogen atoms of OH's in saccharides such as
glucose or the like are substituted with acyl groups, as described
in WO2007/125764, [0042]-[0065]. The amount of the saccharide-type
plasticizer to be added is preferably from 0.1% by mass to less
than 20% by mass relative to the main ingredient, cellulose
acylate, more preferably from 0.1% by mass to less than 10% by
mass, even more preferably from 0.1% by mass to less than 7% by
mass.
(Oligomer-Type Plasticizer)
[0178] As describe in the above, the cellulose acylate film of the
invention preferably contains an oligomer-type plasticizer selected
from oligomers. Preferred examples of the oligomer-type plasticizer
include polycondensates of a diol component and a dicarboxylic acid
component and their derivatives (hereinafter this may be referred
to as "polycondensate ester-type plasticizer"), as well as
oligomers of methyl acrylate (MA) and their derivatives
(hereinafter this may be referred to as "MA oligomer-type
plasticizer").
[0179] The polycondensate ester is an polycondensate ester of a
dicarboxylic acid component and a diol component. The dicarboxylic
acid component may be only one type of a dicarboxylic acid or may
be a mixture of two or more different types of dicarboxylic acids.
Above all, as the dicarboxylic acid component, preferred is a
dicarboxylic acid component containing at least one aromatic
dicarboxylic acid and at least one aliphatic dicarboxylic acid. On
the other hand, the diol component may be only one type of a diol
component or may be a mixture of two or more different types of
diols. Above all, the diol component is preferably ethylene glycol
and/or an aliphatic diol having a mean carbon number of from more
than 2.0 to 3.0.
[0180] Regarding the ratio of the aromatic dicarboxylic acid to the
aliphatic dicarboxylic acid in the dicarboxylic acid component, the
proportion of the aromatic dicarboxylic acid therein is preferably
from 5 to 70 mol %. Within the range, the plasticizer is effective
for reducing the environmental humidity dependence of the optical
properties of film and the plasticizer could be prevented from
bleeding out during film formation. The proportion of the aromatic
dicarboxylic acid in the dicarboxylic acid component is more
preferably from 10 to 60 mol %, even more preferably from 20 to 50
mol %.
[0181] Examples of the aromatic dicarboxylic acid include phthalic
acid, terephthalic acid, isophthalic acid,
1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid,
1,8-naphthalenedicarboxylic acid, 2,8-naphthalenedicarboxylic acid,
2,6-naphthalenedicarboxylic acid, etc.; and preferred are phthalic
acid and terephthalic acid. Examples of the aliphatic dicarboxylic
acid include oxalic acid, malonic acid, succinic acid, maleic acid,
fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic
acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, etc.; and above all, preferred
are succinic acid and adipic acid.
[0182] The diol component is preferably ethylene glycol and/or a
diol having a mean carbon number of from more than 2.0 to 3.0. In
the diol component, the proportion of ethylene glycol is preferably
at least 50 mol %, more preferably at least 75 mol %. The aliphatic
diol may be an alkyl diol or an alicyclic diol, including, for
example, ethylene glycol, 1,2-propanediol, 1,3-propanediol,
1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol,
1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol
(neopentyl glycol), 2,2-diethyl-1,3-propanediol
(3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol
(3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol,
2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol,
2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,
1,12-octadecanediol, diethylene glycol, etc; and preferably, these
are used as a mixture of one or more of them with ethylene
glycol.
[0183] For the diol component, preferred are ethylene glycol,
1,2-propanediol and 1,3-propanediol; and more preferred are
ethylene glycol and 1,2-propanediol.
[0184] The polycondensate ester-type plasticizer is preferably a
derivative of a polycondensate ester in which the terminal OH forms
an ester with a monocarboxylic acid. The monocarboxylic acid for
terminating the terminal OH groups of the ester is preferably an
aliphatic monocarboxylic acid, more preferably acetic acid,
propionic acid, butanoic acid, benzoic acid or their derivative,
even more preferably acetic acid or propionic acid, most preferably
acetic acid. When the carbon number of the monocarboxylic acid for
use to terminate the polycondensate ester is at most 3, then the
loss on heat of the compound is not large and the surface defect of
the film may be reduced. Two or more different types of
monocarboxylic acids may be used as a mixture for the termination.
Preferably, the terminals of the polycondensate ester are
terminated with acetic acid or propionic acid; and more preferably,
the terminals of the polycondensate ester derivative are both
acetyl ester residues formed through termination with acetic
acid.
[0185] Preferably, the polycondensate ester and its derivative are
oligomers having a number-average molecular weight of from 700 to
2000 or so, more preferably from 800 to 1500 or so, even more
preferably from 900 to 1200 or so. The number-average molecular
weight of the polycondensate ester may be measured and evaluated
through gel permeation chromatography.
[0186] Table 5 below shows specific examples of polycondensate
ester-type plasticizers, to which, however, the invention should
not be limited.
TABLE-US-00004 TABLE 5 Dicarboxylic Acid*1) Diol Number- Aromatic
Aliphatic Dicarboxylic Diol Mean Carbon Average Dicarboxylic
Dicarboxylic Acid Ratio Ratio Number of Molecular Acid Acid (mol %)
Aliphatic Diol (mol %) Aliphatic Diol Both Terminals Weight P-1 PA
AA 10/90 ethylene glycol 100 2.0 acetyl ester residue 1000 P-2 PA
AA 25/75 ethylene glycol 100 2.0 acetyl ester residue 1000 P-3 PA
AA 50/50 ethylene glycol 100 2.0 acetyl ester residue 1000 P-4 PA
SA 5/95 ethylene glycol 100 2.0 acetyl ester residue 1000 P-5 PA SA
20/80 ethylene glycol 100 2.0 acetyl ester residue 1000 P-6 TPA AA
15/85 ethylene glycol 100 2.0 acetyl ester residue 1000 P-7 TPA AA
50/50 ethylene glycol 100 2.0 acetyl ester residue 1000 P-8 TPA SA
5/95 ethylene glycol 100 2.0 acetyl ester residue 1000 P-9 TPA SA
10/90 ethylene glycol 100 2.0 acetyl ester residue 1000 P-10 TPA SA
15/85 ethylene glycol 100 2.0 acetyl ester residue 1000 P-11 TPA SA
50/50 ethylene glycol 100 2.0 acetyl ester residue 1000 P-12 TPA SA
70/30 ethylene glycol 100 2.0 acetyl ester residue 1000 P-13 TPA/PA
AA 10/10/80 ethylene glycol 100 2.0 acetyl ester residue 1000 P-14
TPA/PA AA 20/20/60 ethylene glycol 100 2.0 acetyl ester residue
1000 P-15 TPA/PA AA/SA 10/10/40/40 ethylene glycol 100 2.0 acetyl
ester residue 1000 P-16 TPA AA/SA 10/30/60 ethylene glycol 100 2.0
acetyl ester residue 1000 P-17 TPA AA/SA 10/30/60 ethylene
glycol/1,2-propanediol 50/50 2.5 acetyl ester residue 1000 P-18 TPA
AA/SA 10/30/60 1,2-propanediol 100 3.0 acetyl ester residue 1000
P-19 TPA AA/SA 10/30/60 ethylene glycol 100 2.0 acetyl ester
residue 700 P-20 TPA AA/SA 10/30/60 ethylene glycol 100 2.0 acetyl
ester residue 850 P-21 TPA AA/SA 10/30/60 ethylene glycol 100 2.0
acetyl ester residue 1200 P-22 TPA AA/SA 10/30/60 ethylene glycol
100 2.0 acetyl ester residue 1600 P-23 TPA AA/SA 10/30/60 ethylene
glycol 100 2.0 acetyl ester residue 2000 P-24 TPA AA/SA 10/30/60
ethylene glycol 100 2.0 propionyl ester residue 1000 P-25 TPA AA/SA
10/30/60 ethylene glycol 100 2.0 butanoyl ester residue 1000 P-26
TPA AA/SA 10/30/60 ethylene glycol 100 2.0 benzoyl ester residue
1000 P-27 IPA AA/SA 20/40/40 ethylene glycol 100 2.0 acetyl ester
residue 1000 P-28 2.6-NPA AA/SA 20/40/40 ethylene glycol 100 2.0
acetyl ester residue 1200 P-29 1.5-NPA AA/SA 20/40/40 ethylene
glycol 100 2.0 acetyl ester residue 1200 P-30 1.4-NPA AA/SA
20/40/40 ethylene glycol 100 2.0 acetyl ester residue 1200 P-31
1.8-NPA AA/SA 20/40/40 ethylene glycol 100 2.0 acetyl ester residue
1200 P-32 2.8-NPA AA/SA 20/40/40 ethylene glycol 100 2.0 acetyl
ester residue 1200 *1)PA: phthalic acid, TPA: terephthalic acid,
IPA: isophthalic acid, AA: adipic acid, SA: succinic acid, 2,6-NPA:
2,6-naphthalenedicarboxylic acid, 2,8-NPA:
2,8-naphthalenedicarboxylic acid, 1,5-NPA:
1,5-naphthalenedicarboxylic acid, 1,4-NPA:
1,4-naphthalenedicarboxylic acid, 1,8-NPA:
1,8-naphthalenedicarboxylic acid
[0187] The polycondensate ester can be produced with ease according
to any conventional method, for example, according to a
polyesterification, interesterification or thermal-fusing
condensation method of a dicarboxylic acid component and a diol
component, or an interfacial condensation method of an acid
chloride of a dicarboxylic acid component and a glycol.
Polycondensate esters usable in the invention are described in
detail in Koichi Murai, "Plasticizers and their Theory and
Applications" (by Miyuki Shobo, 1st Ed., issued on Mar. 1, 1973).
In addition, also usable herein are materials described JP-A
5-155809, 5-155810, 5-197073, 2006-259494, 7-330670, 2006-342227,
2007-003679.
[0188] The amount of the polycondensate ester-type plasticizer to
be added is preferably from 0.1 to 25% by mass of the amount of the
main ingredient, cellulose acylate, more preferably from 1 to 20%
by mass, even more preferably from 3 to 15% by mass.
[0189] The content of the starting materials and the side products
in the polycondensate ester-type plasticizer, concretely aliphatic
diols, dicarboxylates, diol esters and others, that may be in the
film is preferably less than 1%, more preferably less than 0.5%.
The dicarboxylate includes dimethyl phthalate,
di(hydroxyethyl)phthalate, dimethyl terephthalate,
di(hydroxyethyl)terephthalate, di(hydroxyethyl)adipate,
di(hydroxyethyl)succinate, etc. The diol ester includes ethylene
diacetate, propylene diacetate, etc.
[0190] As the plasticizer for use in the cellulose acylate film of
the invention, also preferred is a methyl methacrylate (MA)
oligomer-type plasticizer. Combination of the MA oligomer-type
plasticizer and the above-mentioned saccharide-type plasticizer is
also preferred. In the mode of combination use, the ratio by mass
of the MA oligomer-type plasticizer to the saccharide-type
plasticizer is preferably from 1/2 to 1/5, more preferably from 1/3
to 1/4. One example of the MA oligomer-type plasticizer is an
oligomer containing the following recurring unit:
##STR00083##
[0191] The weight-average molecular weight is preferably from 500
to 2000 or so, more preferably from 700 to 1500 or so, even more
preferably from 800 to 1200 or so.
[0192] The MA oligomer-type plasticizer may be an MA homo-oligomer
as well as an oligomer comprising the above-mentioned recurring
unit derived from MA and at least one other recurring unit derived
from any other monomer. Examples of the other monomer include ethyl
acrylate, propyl (i-, n-) acrylate, butyl (n-, i-, s-, t-)
acrylate, pentyl (n-, i-, s-) acrylate, hexyl (n-, i-) acrylate,
heptyl (n-, i-) acrylate, octyl (n-, i-) acrylate, nonyl (n-, i-)
acrylate, myristyl (n-, i-) acrylate, (2-ethylhexyl)acrylate,
(.epsilon.-caprolactone) acrylate, (2-hydroxyethyl)acrylate,
(2-hydroxypropyl)acrylate, (3-hydroxypropyl)acrylate,
(4-hydroxybutyl)acrylate, (2-hydroxybutyl)acrylate,
(2-methoxyethyl)acrylate, (2-ethoxyethyl)acrylate, and
corresponding methacrylate monomers. In addition, also usable are
aromatic ring-having monomers such as styrene, methylstyrene,
hydroxystyrene, etc. As the other monomer, preferred are
non-aromatic acrylate monomers and methacrylate monomers.
[0193] In the case where the MA oligomer-type plasticizer is an
oligomer having two or more different types of recurring units, the
oligomer preferably comprises X (hydrophilic group-having monomer
component) and Y (hydrophilic group-free monomer component), in
which the ratio (by mol) of X/Y is from 1/1 to 1/99.
[0194] The MA oligomer may be produced with reference to the method
described in JP-A 2003-12859.
(Polymer Plasticizer)
[0195] The cellulose acylate film of the invention may contain any
other polymer plasticizer along with or in place of any one of the
above-mentioned saccharide-type plasticizer, polycondensate
ester-type plasticizer and MMA oligomer-type plasticizer. The other
polymer plasticizer includes polyester-polyurethane plasticizers,
aliphatic hydrocarbon polymers, alicyclic hydrocarbon polymers;
vinylic polymers such as polyvinyl isobutyl ether,
poly-N-vinylpyrrolidone, etc.; styrenic polymers such as
polystyrene, poly-4-hydroxystyrene, etc.; polyethers such as
polyethylene oxide, polypropylene oxide, etc.; polyamides,
polyurethanes, polyureas, phenol-formaldehyde condensates,
urea-formaldehyde condensates, polyvinyl acetate, etc.
(Compound Having at Least Two Aromatic Rings)
[0196] The cellulose acylate film of the invention may contain a
compound having at least two aromatic rings, not contradictory to
the scope and the sprit of the invention. The compound has an
effect of regulating the optical properties of the cellulose
acylate film. For example, when the cellulose acylate film of the
invention is used as an optically-compensatory film, it is
effectively stretched for regulating the optical properties,
especially Re thereof to be on a desired level. For increasing Re
thereof, the in-plane refractive anisotropy of the film must be
increased, for which one method comprises regulating the main chain
orientation by stretching. As combined with stretching, a compound
having a large refractivity anisotropy may be added to the film for
further increasing the refractive anisotropy of the film. For
example, when the film to which a compound having at least two
aromatic rings is added as an additive thereto is stretched, the
main chain of the polymer constituting the film is oriented, and
with that, the compound itself becomes well orientable and the film
may be regulated to have desired optical properties with ease.
[0197] The compound having at least two aromatic rings includes,
for example, triazine compounds as in JP-A 2003-344655, rod-shaped
compounds as in JP-A 2002-363343, liquid crystalline compounds as
in JP-A 2005-134884 and 2007-119737, etc. More preferred are
triazine compounds and rod-shaped compounds. Two or more different
types of compounds having at least two aromatic rings may be used,
as combined. The molecular weight of the compound having at least
two aromatic rings is preferably from 300 to 1200 or so, more
preferably from 400 to 1000.
[0198] The amount of the compound having at least two aromatic
rings to be added is preferably from 0.05% to 10% in terms of the
ratio by mass to cellulose acylate resin, more preferably from 0.5%
to 8%, even more preferably from 1% to 5%. The compound having two
aromatic rings may serve also as the compound capable of forming a
hydrogen bond for use in the invention. On the other hand, when the
compound having two aromatic rings has a 1,3,5-triazine ring
structure but does not satisfy any one of the formulae (A-1) to
(H-1), then the amount of the compound having two aromatic rings to
be added is preferably from 0.05% to 10% in terms of the ratio by
mass to cellulose acylate resin, more preferably from 0.5% to 8%,
even more preferably from 1% to 5% from the viewpoint of the
humidity dependence improvability of the compound.
(Optical Anisotropy Regulator)
[0199] The cellulose acylate film of the invention may contain an
optical anisotropy regulator. For example, examples of the
regulator include "Rth-reducing compounds" described in JP-A
2006-30937, pp. 23-72.
(Matting Agent Particles)
[0200] A matting agent may be added to the cellulose acylate film.
Particles usable as the matting agent include silicon dioxide,
titanium dioxide, aluminium oxide, zirconium oxide, calcium
carbonate, talc, clay, fired kaolin, fired calcium silicate,
calcium silicate hydrate, aluminium silicate, magnesium silicate
and calcium phosphate. As the particles, preferred are
silicon-containing ones as lowering the turbidity of the film, and
more preferred is silicon dioxide.
[0201] As silicon dioxide particles, for example, usable are
commercial products such as Aerosil R972, R972V, R974, R812, 200,
200V, 300, R202, OX50, TT600 (all by Nippon Aerosil), etc.
Zirconium oxide particles are commercially available, for example,
as Aerosil R972 and R811 (both by Nippon Aerosil), and are usable
herein.
[0202] In producing a cellulose acylate film containing particles
having a small secondary mean particle size, usable is a dispersion
of the particles. Some methods may be taken into consideration in
preparing a dispersion of particles. For example, there is
mentioned a method where a dispersion of particles is previously
prepared by stirring and mixing a solvent and particles, and the
particle dispersion is added to a small amount of a cellulose
acylate solution separately prepared and dissolved therein with
stirring, and then this is further mixed with a main cellulose
acylate dope liquid. According to the method, the silicon dioxide
particles are well dispersible and the dispersed silicon dioxide
particles hardly reaggregate, and the method is a favorable method.
Apart from this, there may be mentioned another method in which a
small amount of cellulose acylate is added to a solvent and
dissolved therein with stirring, and particles are added thereto
and dispersed with a disperser to prepare a particles-added liquid,
and the particles-added liquid is well mixed with a dope liquid
using an in-line mixer. Any of those methods is employable herein,
and the invention is not limited to these methods.
[0203] The solvent to be used in the above preparation methods may
be a lower alcohol, preferably methyl alcohol, ethyl alcohol,
propyl alcohol, isopropyl alcohol, butyl alcohol, etc. Not
specifically defined, any other solvent than such a lower alcohol
is also usable; for which preferred are solvents for use in
cellulose acylate film formation.
(Low-Molecular Plasticizer, Degradation Inhibitor, Release
Agent)
[0204] Various other additives than those mentioned above (e.g.,
low-molecular plasticizer, UV inhibitor, degradation inhibitor,
release agent, IR absorbent, etc.) may be added to the cellulose
acylate film in the process of producing the film, depending on the
applications of the film. The additives may be solid or oily, or
that is, they are not specifically defined in point of their
melting point and boiling point thereof. For example, for the
additive, UV absorbents at 20.degree. C. or lower and at 20.degree.
C. or higher may be mixed, or plasticizers may also be mixed in the
same manner. For example, these are described in JP-A 2001-151901.
IR absorbent dyes are described in, for example, JP-A 2001-194522.
The time at which the additive is added may be in any stage in the
step of dope preparation; however, the additive may be added in the
final stage of the dope preparation step. Not specifically defined,
the amount of the material to be added may be any one capable
expressing the function thereof. In the case where the cellulose
acylate film is formed of plural layers, then the type and the
amount of the additive to be added to the constitutive layers may
differ. For example, as in JP-A 2001-151902, the related technique
is known in the art. Regarding the details of the additives, the
materials described in Hatsumei Kyokai Disclosure Bulletin No.
2001-1745, pp. 16-22, (published in Mar. 15, 2001 by Hatsumei
Kyokai) are preferred for use in the invention.
(1-4) Production Method for Cellulose Acylate Film:
[0205] The cellulose acylate film of the invention is preferably
produced according to a solution-casting method (solvent-casting
method). According to a solvent-casting method, a cellulose acylate
is dissolved in an organic solvent to prepare a dope, and the
resulting dope is cast onto the surface of a support formed of a
metal or the like, and dried into a film, and thereafter the film
is peeled away from the support surface, and stretched.
[0206] For production examples for cellulose acylate film according
to a solvent casting method, reference may be made to U.S. Pat.
Nos. 2,336,310, 2,367,603, 2,492,078, 2,492,977, 2,492,978,
2,607,704, 2,739,069 and 2,739,070; British Patent 640731 and
736892; JP-B 45-4554 and 49-5614; JP-A 60-176834, 60-203430 and
62-115035, etc. The cellulose acylate film may be stretched.
Regarding the method and the condition for the stretching
treatment, for example, reference may be made to the examples
described in JP-A 62-115035, 4-152125, 4-284211, 4-298310,
11-48271, etc.
(1-5) Characteristics of Cellulose Acylate Film: (Re and Rth)
[0207] The preferred range of the optical characteristics of the
cellulose acylate film of the invention may change depending on the
use of the film.
[0208] In an embodiment where the film is used in a VA-mode liquid
crystal display device, preferably, its Re(589) is from 30 nm to
200 nm, more preferably from 30 nm to 150 nm, even more preferably
from 40 nm to 100 nm, and its Rth(589) is from 70 nm to 400 nm,
more preferably from 100 nm to 300 nm, even more preferably from
100 nm to 250 nm.
[0209] In an embodiment where the film is used in a TN-mode liquid
crystal display device, preferably, its Re(589) is from 0 nm to 100
nm, more preferably from 20 nm to 90 nm, even more preferably from
50 nm to 80 nm, and its Rth(589) is from 20 nm to 200 nm, more
preferably from 30 nm to 150 nm, even more preferably from 40 nm to
120 nm.
(Humidity Dependence of Re and Humidity Dependence of Rth)
[0210] Regarding the cellulose acylate film of the invention, the
fluctuation between its Re and Rth when the film is conditioned at
25.degree. C. and at a relative humidity of 10% for 12 hours
(hereinafter these may be referred to as Re(10%) and Rth(10%)) and
its Re and Rth conditioned at 25.degree. C. and a relative humidity
of 80% for 12 hours (hereinafter these may be referred to as
Re(80%) and Rth(80%)) is small. When the humidity dependence of the
optical characteristic of the film is enhanced in that manner, then
Re and Rth fluctuation of the film under the condition under which
the humidity of the usage environment varies can be prevented and
the film can exhibit the retardation falling within the
above-mentioned preferred range. Accordingly, the invention can
provide a cellulose acylate film favorable for use under the
condition under which the humidity of the usage environment
varies.
[0211] Preferably, the cellulose acylate film of the invention has
an Re humidity dependence (.DELTA.Re=Re(10%)-Re(80%)) of less than
10 nm, more preferably at most 8 nm, even more preferably at most 5
nm.
[0212] Preferably, the cellulose acylate film of the invention has
an Rth humidity dependence (.DELTA.Rth=Rth(10%)-Rth(80%)) of at
most 20.5 nm, more preferably at most 18.5 nm, even more preferably
at most 14.5 nm.
(Film Thickness)
[0213] In an embodiment where the cellulose acylate film of the
invention is used as a part in a device that is desired to have a
thinned body, for example, as a part of a liquid crystal display
device or the like, the film is preferably thinner. However, if too
thin, the film could not exhibit the optical characteristics
necessary for the use. In an embodiment where the film of the
invention is used as an optical compensatory film in a liquid
crystal display device, or as a protective film for a polarizer,
the film thickness is preferably from 20 to 80 .mu.m or so, more
preferably from 25 to 70 .mu.m or so, even more preferably from 30
to 60 .mu.m or so.
(Haze)
[0214] The cellulose acylate film of the invention preferably has a
low haze. The film having a low haze is favorable since it does not
lower the contrast on the front (in the normal direction relative
to the panel surface) of a liquid crystal display device comprising
it.
(Axial Misalignment)
[0215] When a film having a slow axis in the direction
perpendicular to the film-traveling direction, or that is, in the
cross direction of the film is stretched with a tenter, then the
slow axis of the film may be deviated (bowed) more on the outer
side thereof, even though the slow axis thereof could be in that
perpendicular direction in the center of the film. The width of the
film produced according to a solvent casting method means the
length of the film in the direction perpendicular to the
dope-casting direction.
[0216] Preferably, the axial misalignment of the slow axis of the
cellulose acylate film of the invention is as small as possible in
the entire width of the film.
[0217] The slow axis of the film may be determined simultaneously
with determination of the in-plane retardation thereof. Concretely,
a small test piece is cut out of the film, completely in parallel
to the end thereof in the film-traveling direction, and this is
analyzed with KOBRA 21ADH or WR for in-plane retardation
measurement, and at the same time, the slow axis of the film may be
determined.
2. Use of Cellulose Acylate Film:
[0218] The cellulose acylate film of the invention has many
applications. For example, it may be used as a retardation film
(hereinafter this may be referred to as optical compensatory film)
in liquid crystal display devices, as a protective film of
polarizers, etc.
(Retardation Film)
[0219] The cellulose acylate film of the invention may be used as a
retardation film. "Retardation film or optical compensatory film"
means an optical material having optical anisotropy generally for
use in display devices such as liquid crystal display devices,
etc., and this has the same meaning as that of an optical
compensatory sheet or the like. In a liquid crystal display device,
such an optical compensatory film is used for the purpose of
enhancing the contrast of the display panel, for enlarging the
viewing angle and for solving a problem of color shift.
[0220] Plural cellulose acylate films of the invention may be
laminated, or the cellulose acylate film of the invention may be
laminated with any other film than the film of the invention,
thereby suitably regulating Re and Rth of the resulting laminate to
be an optical compensatory film. The film lamination may be
attained with a sticking paste or an adhesive.
(Polarizer)
[0221] The cellulose acylate film of the invention may be used as a
protective film for polarizers, and the invention provides a
polarizer comprising the film. One example of the polarizer of the
invention comprises a polarizing film and two protective films
(transparent films) for protecting both surfaces of the polarizing
film, in which the cellulose acylate film of the invention is used
as at least one of the polarizer-protective films. In an embodiment
where the cellulose acylate film of the invention is used as a
support and an optically-anisotropic layer of a liquid crystal
composition is formed on the surface of the support, and where the
cellulose acylate film is used as a protective film for a
polarizer, it is desirable that the back side (on which the
optically-anisotropic layer is not formed) of the cellulose acylate
film of the invention serving as a support is stuck to the surface
of the polarizing film.
[0222] In the case where the cellulose acylate film of the
invention is used as a protective film for the polarizer, the
cellulose acylate film of the invention is preferably
hydrophilicated through the above-mentioned surface-treatment
(e.g., as described in JP-A 6-94915 and 6-118232), and for example,
the film is preferably processed for glow discharge treatment,
corona discharge treatment, or alkali saponification. In
particular, the surface treatment of the film is most preferably
alkali saponification.
[0223] As the polarizing film, for example, usable is a film
produced by dipping a polyvinyl alcohol film in an iodine solution
and stretching it. In the case where the polarizing film produced
by dipping a polyvinyl alcohol film in an iodine solution and
stretching it is used, the surface-treated surface of the cellulose
acylate film of the invention may be directly stuck to both
surfaces of the polarizing film with an adhesive. In the production
method of the invention, it is desirable that the cellulose acylate
film is directly stuck to the polarizing film in the manner as
above. As the adhesive, usable is an aqueous solution of polyvinyl
alcohol or polyvinyl acetal (e.g., polyvinyl butyral) or a latex of
a vinylic polymer (e.g., polybutyl acrylate). Especially preferred
as the adhesive is an aqueous solution of a completely-saponified
polyvinyl alcohol.
[0224] In general, in a liquid crystal display device, a liquid
crystal cell is disposed between two polarizers. Therefore, the
device has four polarizer-protective films. The cellulose acylate
film of the invention may be used as any of those four
polarizer-protective films, but the cellulose acylate film of the
invention is especially useful as the protective film to be
disposed between the polarizing film and the liquid crystal layer
(liquid crystal cell) in the liquid crystal display device. As the
protective film to be disposed on the side of the polarizing film
opposite to the side of the cellulose acylate film of the
invention, a transparent hard coat layer, an antiglare layer, an
antireflection layer or the like may be disposed, and in
particular, the film of the invention is favorable as the
polarizer-protective film to be disposed as the outermost surface
layer on the display panel side of the liquid crystal display
device.
(Liquid Crystal Display Device)
[0225] The cellulose acylate film of the invention and the
optically-compensatory film and the polarizer comprising the film
can be used in various display modes of liquid crystal display
devices. Various liquid crystal modes where the film of the
invention can be used are described. Above all, the cellulose
acylate film of the invention and the optically-compensatory film
and the polarizer comprising the film are favorably used in VA-mode
liquid crystal display devices. The liquid crystal display devices
may be any of transmission-mode, reflection-mode or
semitransmission-mode devices.
[0226] FIG. 1 shows a schematic cross-sectional view of one example
of a liquid crystal display device of the invention. In FIG. 1, the
upper side is a viewers' side (panel side), and the lower side is a
backlight side.
[0227] The VA-mode liquid crystal display device of in FIG. 1
comprises a liquid crystal cell LC (comprising an upper substrate
1, a lower substrate 3 and a liquid crystal layer 5), and a pair of
an upper polarizer P1 and a lower polarizer P2 disposed to sandwich
the liquid crystal cell LC therebetween. In general, polarizing
films are incorporated into the liquid crystal display device as
polarizers having a protective film on both surfaces thereof;
however, in FIG. 1, the outer protective film of the polarizing
film is omitted. The polarizers P1 and P2 each have a polarizing
film 8a and 8b, respectively; and they are so disposed that the
absorption axes 9a and 9b thereof are perpendicular to each other.
The liquid crystal cell LC is a VA-mode liquid crystal cell, and at
the time of black level of display, the liquid crystal layer 5 is
in homeotropic alignment as in FIG. 1. The upper substrate 1 and
the lower substrate 3 each have an alignment film (not shown) and
an electrode layer (not shown) on the inner surface thereof; and
the substrate 1 has a color filter layer (not shown) on the
viewers' side inner surface thereof.
[0228] Between the upper substrate 1 and the upper polarizing film
8a, and between the lower substrate 3 and the lower polarizing film
8b, disposed are retardation films 10a and 10b, respectively. The
retardation films 10a and 10b are cellulose acylate films of the
invention. The retardation films 10a and 10b are so disposed that
the in-plane slow axes 11a and 11b thereof could be perpendicular
to the absorption axes 9a and 9b of the upper polarizing film 8a
and the lower polarizing film 8b, respectively. Specifically, the
retardation films 10a and 10b are so disposed that their slow axes
are perpendicular to each other. The retardations films 10a and 10b
each comprising the cellulose acylate film of the invention
contribute toward reducing the light leakage and the color shift
that may occur in oblique directions at the time of black level of
display.
(Hard Coat Film, Antiglare Film, Antireflection Film)
[0229] The cellulose acylate film of the invention may be applied
to a hard coat film, an antiglare film, or an antireflection film,
as the case may be. For the purpose of enhancing the visibility of
flat panel displays such as LCD, PDP, CRT, EL and the like, any or
all of a hard coat layer, an antiglare layer and an antireflection
layer may be given to one or both surfaces of the cellulose acylate
film of the invention. Preferred embodiments of such antiglare film
and antireflection film are described in detail in Hatsumei Kyokai
Disclosure Bulletin (No. 2001-1745, published on Mar. 15, 2001 by
Hatsumei Kyokai), pp. 54-57, and are favorably applicable to the
cellulose acylate film of the invention.
EXAMPLES
[0230] The characteristics of the invention are described more
concretely with reference to the following Examples. In the
following Examples, the material used, its amount and the ratio,
the details of the treatment and the treatment process may be
suitably modified or changed. Accordingly, the invention should not
be limitatively interpreted by the Examples mentioned below.
1. Formation of Cellulose Acylate Film:
[0231] Cellulose acylate resin A (100 parts by mass) was mixed in a
solvent of methylene chloride (410 parts by mass) and ethanol (45
parts by mass) to prepare a cellulose acylate (concretely,
cellulose acetate propionate) solution. The solution was cast with
a band caster, the resulting web was peeled away from the band, and
thereafter this was stretched in TD (transverse direction of the
film) by 35% at 145.degree. C., then dried to give a cellulose
acylate film (concretely, cellulose acetate propionate film) having
a thickness of 50 .mu.m. This is a film 101.
[0232] Films 115, 121, 127, 131 and 135 were produced in the same
manner as that for the film 101, for which, however, the type of
the cellulose acylate was changed from A to that in the Table 6
below.
(Evaluation of Optical Properties)
[0233] Thus prepared Films 101, 115, 121, 127, 131 and 135
containing no additives were sampled three times at three points in
the cross direction (center, two edges (at the position of 5% of
the overall width from each side)) at intervals of 10 m in the
machine direction, thereby preparing 9 samples each having a size
of 3 cm square. The samples were tested according to the method
mentioned below, and the data were averaged.
[0234] The sample film was conditioned at 25.degree. C. and a
relative humidity of 60% for 24 hours, then using an automatic
birefringence meter (KOBRA-21ADH by Oji Scientific Instruments), it
was analyzed at 25.degree. C. and a relative humidity of 60% for
the retardation at a wavelength of 590 nm in the vertical direction
to the film surface, and in oblique directions tilted from the film
surface normal line at intervals of 10.degree. within a range of
+50.degree. to -50.degree.. The in-plane retardation (Re) and the
thickness-direction retardation (Rth) of each film sample were thus
computed.
[0235] The results are shown in Table 6 below.
[0236] The humidity-dependent change of the retardation of the film
was determined as follows: The film was analyzed in the same manner
as above except that the film was conditioned at 25.degree. C. and
at a relative humidity of 10% for 12 hours and Re and Rth of the
film were measured (Re(10%) and Rth(10%)). The film was analyzed
also in the same manner as above except that film was conditioned
at 25.degree. C. and at a relative humidity of 80% for 12 hours and
Re and Rth of the film were measured (Re(80%) and Rth(80%)). More
specifically, the Re humidity dependence (.DELTA.Re.sub.0) and the
Rth humidity dependence (.DELTA.Rth.sub.0) of Films 101, 115, 121,
127, 131 and 135 containing no additives are obtained from the
following formulae:
.DELTA.Re=Re(10%)-Re(80%)
.DELTA.Rth=Rth(10%)-Rth(80%)
[0237] The results are shown in Table 6 below.
[0238] Other films were produced in the manner mentioned below.
Concretely, films 102 to 114 were produced in the same manner as
that for the film 101, to which, however, the additive shown in
Table 6 below was added in the amount shown therein. Similarly,
films 116 to 120 were produced in the same manner as that for the
film 115, to which, however, the additive shown in Table 6 below
was added in the amount shown therein; films 122 to 126 were
produced in the same manner as that for the film 121, to which,
however, the additive shown in Table 6 below was added in the
amount shown therein; films 128 to 130 were produced in the same
manner as that for the film 127, to which, however, the additive
shown in Table 6 below was added in the amount shown therein; films
132 to 134 were produced in the same manner as that for the film
131, to which, however, the additive shown in Table 6 below was
added in the amount shown therein; and films 136 was produced in
the same manner as that for the film 135, to which, however, the
additive shown in Table 6 below was added in the amount shown
therein. The structures of the compounds A-11 to A-16 and the
comparative compounds T and U-1 to U-3 used as the additive are
shown below.
##STR00084## ##STR00085##
[0239] Thus produced, the additive-containing films of Examples and
Comparative Examples were analyzed for the physical properties
thereof, like the additive-free films (films 101, 115, 121, 127,
131 and 135). Of the additive-containing films of Examples and
Comparative Examples, the humidity dependence of the retardation
was computed as .DELTA.Re={Re(10%) of film}-{Re(80%) of film} and
.DELTA.Rth={Rth(10%) of film}-{Rth(80%) of film}.
[0240] From .DELTA.Re.sub.0 of the additive-free film and .DELTA.Re
of the additive-containing films of Examples and Comparative
Examples in the series of the samples formed of the same type of
cellulose acylate resin, .DELTA.Re.sub.0-.DELTA.Re was computed.
Similarly, .DELTA.Rth.sub.0-.DELTA.Rth was computed in the series
of the samples formed of the same type of cellulose acylate
resin.
[0241] These results are shown in Table 6 below.
TABLE-US-00005 TABLE 6 Additive Cellulose Acylate Resin Amount
Degree of Degree of Total degree .DELTA.Re.sub.0 .DELTA.Re.sub.0
added acetyl propionyl of acyl or .DELTA.Re.sub.0 - or
.DELTA.Rth.sub.0 - Com- [part substi- substi- substi- Re .DELTA.Re
.DELTA.Re Rth .DELTA.Re .DELTA.Rth Film pound by mass] Type tution
tution tution (nm) [nm] [nm] [nm] [nm] [nm] Remarks 101 -- 0 A 1.9
0.6 2.5 32.1 13.3 -- 108.4 32.0 -- comparative example 102 1 4 A
1.9 0.6 2.5 41.7 6.3 7.0 160.0 13.3 18.7 example of the invention
103 1 8 A 1.9 0.6 2.5 50.1 3.0 10.3 185.0 6.5 25.5 example of the
invention 104 2 4 A 1.9 0.6 2.5 35.2 5.8 7.5 96.3 11.1 20.9 example
of the invention 105 3 4 A 1.9 0.6 2.5 31.7 6.3 7.0 88.3 13.0 19.0
example of the invention 106 3 8 A 1.9 0.6 2.5 35.0 4.4 8.9 70.1
7.0 25.0 example of the invention 107 3 12 A 1.9 0.6 2.5 36.2 2.2
11.1 62.0 5.0 27.0 example of the invention 108 4 8 A 1.9 0.6 2.5
30.1 4.1 9.2 79.7 8.0 24.0 example of the invention 109 5 4 A 1.9
0.6 2.5 32.3 6.1 7.2 85.5 13.0 19.0 example of the invention 110 6
8 A 1.9 0.6 2.5 43.9 5.0 8.3 138.0 14.1 17.9 example of the
invention 111 8 4 A 1.9 0.6 2.5 46.0 11.5 1.8 135.0 25.0 7.0
comparative example 112 9 4 A 1.9 0.6 2.5 64.2 10.3 3.0 175.6 23.2
8.8 comparative example 113 9 8 A 1.9 0.6 2.5 90.2 8.9 4.4 218.9
20.9 11.1 comparative example 114 11 4 A 1.9 0.6 2.5 48.8 11.2 2.1
141.3 23.9 8.1 comparative example 115 -- 0 B 1.8 0.6 2.4 42.7 15.2
-- 160.2 35.0 -- comparative example 116 6 4 B 1.8 0.6 2.4 38.0 8.2
7.0 195.4 16.8 18.2 example of the invention 117 6 8 B 1.8 0.6 2.4
49.9 4.8 10.4 212.7 12.0 23.0 example of the invention 118 7 4 B
1.8 0.6 2.4 32.0 9.0 6.2 100.8 14.1 20.9 example of the invention
119 7 8 B 1.8 0.6 2.4 31.3 4.5 10.7 92.4 7.4 27.7 example of the
invention 120 10 4 B 1.8 0.6 2.4 79.1 11.8 3.4 240.9 28.5 6.5
example of the invention 121 -- 0 C 1.6 0.7 2.3 49.8 17.3 -- 194.1
35.2 -- comparative example 122 1 4 C 1.6 0.7 2.3 58.3 9.3 8.0
219.3 15.3 19.9 example of the invention 123 1 8 C 1.6 0.7 2.3 63.8
3.2 14.1 233.3 9.8 25.4 example of the invention 124 3 4 C 1.6 0.7
2.3 51.9 8.4 8.9 162.0 14.4 20.8 example of the invention 125 3 8 C
1.6 0.7 2.3 55.0 3.3 14.1 140.0 7.3 27.9 example of the invention
126 8 8 C 1.6 0.7 2.3 77.0 13.3 4.0 240.0 28.0 7.2 comparative
example 127 -- 0 D 1.5 0.7 2.2 52.3 17.0 -- 219.1 38.3 --
comparative example 128 1 4 D 1.5 0.7 2.2 73.4 9.4 7.6 249.6 18.2
20.1 example of the invention 129 1 8 D 1.5 0.7 2.2 89.3 3.3 13.7
275.4 9.9 28.4 example of the invention 130 9 4 D 1.5 0.7 2.2 99.1
13.0 4.0 330.5 28.4 9.9 comparative example 131 -- 0 E 2.1 0.6 2.7
20.7 9.8 -- 96.0 24.2 -- comparative example 132 1 4 E 2.1 0.6 2.7
31.6 4.6 5.0 130.3 12.1 12.1 example of the invention 133 1 8 E 2.1
0.6 2.7 45.3 2.4 7.4 155.3 6.2 18.0 example of the invention 134 6
8 E 2.1 0.6 2.7 30.3 3.3 6.5 113.4 8.5 15.7 example of the
invention 135 -- 0 F 2.4 0.4 2.8 14.6 8.1 -- 71.9 27.2 --
comparative example 136 1 4 F 2.4 0.4 2.8 24.0 3.2 4.9 82.6 13.9
13.3 comparative example
[0242] From the results in the above Table 6, it is known that the
films of the invention, to which the compound capable of forming a
hydrogen bond had been added, were all improved in point of the
humidity dependence of retardation, as compared with the
comparative films to which the compound capable of forming a
hydrogen bond had not been added. In addition, it is also known
that the comparative films of cellulose acylate resin to which any
of the comparative compounds T and U-1 to U-3 had been added were
still unsatisfactory in point of the humidity dependence
improvement.
Synthesis Example
Synthesis of the Compound of the Formula (A-2)
[0243] The compounds of capable of forming a hydrogen bond having
the following structures which are represented by the formula (A-2)
and can be used in the invention.
##STR00086## ##STR00087## ##STR00088##
Synthesis of Compound (3-1)
[0244] Benzoyl chloride (9.9 g, 70 mmol) was added to a solution of
acetoguanamine (10 g, 32 mmol) in pyridine (50 ml) and the mixture
was heated for reflux for 8 hours. Temperature of the reaction
mixture was dropped to a room temperature and ethyl acetate and
water were added to separate phases. The organic phase was washed
with 1N hydrochloric acid and then water. The organic phase was
dried with magnesium sulfate and the solvent was distilled off
under a reduced pressure. The resultant was purified by a column
chromatography to obtain the compound (3-1).
[0245] The NMR spectrum data of the obtained Compound (3-1) were as
follows:
[0246] .sup.1H-NMR (solvent: DMSO-d6, standard: tetramethylsilane)
.delta. (ppm): 2.50 (3H, s), 7.45-7.55 (4H, m), 7.60-7.65 (2H, m),
7.90-8.00 (4H, m), 11.20 (2H, s)
Synthesis of Compound (3-2)
[0247] Compound (3-2) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed from
benzoyl chloride to o-methylbenzoyl chloride.
[0248] The NMR spectrum data of the obtained Compound (3-2) were as
follows:
[0249] .sup.1H-NMR (solvent: CDCl, standard: tetramethylsilane)
.delta. (ppm): 2.50 (6H, s), 2.60 (3H, s), 7.20-7.30 (4H, m),
7.35-7.45 (2H, m), 7.50-7.60 (2H, m), 8.55 (2H, s)
Synthesis of Compound (3-3)
[0250] Compound (3-3) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed from
benzoyl chloride to p-methylbenzoyl chloride.
[0251] The NMR spectrum data of the obtained Compound (3-3) were as
follows:
[0252] .sup.1H-NMR (solvent: DMSO-d6, standard: tetramethylsilane)
.delta. (ppm): 2.35 (6H, s), 2.50 (3H, s), 7.30 (4H, d), 7.85 (4H,
d), 11.10 (2H, s)
Synthesis of Compound (3-4)
[0253] Compound (3-4) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed from
benzoyl chloride to p-methoxyl benzoyl chloride.
[0254] The NMR spectrum data of the obtained Compound (3-4) were as
follows:
[0255] .sup.1H-NMR (solvent: DMSO-d6, standard: tetramethylsilane)
.delta. (ppm): 2.50 (3H, s), 3.80 (6H, s), 7.00 (4H, d), 7.95 (4H,
d), 11.00 (2H, s)
Synthesis of Compound (3-5)
[0256] Compound (3-5) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed from
benzoyl chloride to m-methoxylbenzoyl chloride.
[0257] The NMR spectrum data of the obtained Compound (3-5) were as
follows:
[0258] .sup.1H-NMR (solvent: DMSO-d6, standard: tetramethylsilane)
.delta. (ppm): 2.50 (3H, s), 3.80 (6H, s), 7.10-7.20 (2H, m),
7.35-7.45 (2H, m), 7.50-7.60 (4H, m), 11.00 (2H, s)
Synthesis of Compound (3-6)
[0259] Compound (3-6) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed from
benzoyl chloride to p-tert-butylbenzoyl chloride.
[0260] The NMR spectrum data of the obtained Compound (3-6) were as
follows:
[0261] .sup.1H-NMR (solvent: DMSO-d6, standard: tetramethylsilane)
.delta. (ppm): 1.30 (18H, s), 2.50 (3H, s), 7.55 (4H, d), 7.95 (4H,
d), 11.00 (2H, s)
Synthesis of Compound (3-7)
[0262] Compound (3-7) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed from
benzoyl chloride to m-methylbenzoyl chloride.
[0263] The NMR spectrum data of the obtained Compound (3-7) were as
follows:
[0264] .sup.1H-NMR (solvent: CDCl.sub.3, standard:
tetramethylsilane) .delta. (ppm): 2.40 (6H, s), 2.65 (3H, s),
7.35-7.45 (4H, m), 7.70-7.80 (4H, m), 8.80 (2H, s)
Synthesis of Compound (3-8)
[0265] Compound (3-8) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed from
benzoyl chloride to p-chlorobenzoyl chloride.
[0266] The NMR spectrum data of the obtained Compound (3-8) were as
follows:
[0267] .sup.1H-NMR (solvent: CDCl.sub.3, standard:
tetramethylsilane) .delta. (ppm): 2.60 (3H, s), 7.40-7.50 (4H, m),
7.90-8.00 (4H, m), 9.10 (2H, s)
Synthesis of Compound (3-9)
[0268] Compound (3-9) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed from
benzoyl chloride to o-chlorobenzoyl chloride.
[0269] The NMR spectrum data of the obtained Compound (3-9) were as
follows:
[0270] .sup.1H-NMR (solvent: CDCl.sub.3, standard:
tetramethylsilane) .delta. (ppm): 2.50 (3H, s), 7.30-7.50 (6H, m),
7.60-7.70 (2H, m), 8.95 (2H, s)
Synthesis of Compound (3-10)
[0271] Compound (3-10) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed from
benzoyl chloride to m-chlorobenzoyl chloride.
[0272] The NMR spectrum data of the obtained Compound (3-10) were
as follows:
[0273] .sup.1H-NMR (solvent: CDCl.sub.3, standard:
tetramethylsilane) .delta. (ppm): 2.50 (3H, s), 7.55 (2H, m), 7.70
(2H, m), 7.90 (2H, m), 8.00 (2H, s), 11.35 (2H, s)
Synthesis of Compound (3-11)
[0274] Compound (3-11) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed from
benzoyl chloride to o-methoxybenzoyl chloride.
[0275] The NMR spectrum data of the obtained Compound (3-11) were
as follows:
[0276] .sup.1H-NMR (solvent: DMSO-d6, standard: tetramethylsilane)
.delta. (ppm): 2.40 (3H, s), 3.80 (6H, s), 7.00-7.20 (4H, m), 7.55
(2H, m), 7.65 (2H, m), 10.70 (2H, s)
Synthesis of Compound (3-12)
[0277] Compound (3-12) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed. The
structure of the obtained compound was confirmed through MS
spectrometry.
Synthesis of Compound (3-13)
[0278] Compound (3-13) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed. The
structure of the obtained compound was confirmed through MS
spectrometry.
Synthesis of Compound (3-14)
[0279] Compound (3-14) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed. The
NMR spectrum data of the obtained Compound (3-14) were as
follows:
[0280] .sup.1H-NMR (solvent: DMSO-d6, standard: tetramethylsilane)
.delta. (ppm): 2.40 (3H, s), 4.00 (4H, s), 7.20-7.30 (10H, m),
10.90 (2H, s)
Synthesis of Compound (3-15)
[0281] Compound (3-15) was synthesized by the synthetic process of
Compound (3-1) except that the starting material was changed. The
NMR spectrum data of the obtained Compound (3-15) were as
follows:
[0282] .sup.1H-NMR (solvent: DMSO-d6, standard: tetramethylsilane)
.delta.(ppm): 2.40 (3H, s), 3.80 (3H, s), 7.15 (1H, m), 7.35-7.55
(5H, m), 7.75 (2H, m), 11.10 (1H, s), 11.20 (1H, s)
Synthesis of Compound (3-16)
[0283] Compound (3-16) was synthesized by the synthetic process of
Compound (3-1) except that benzoguanamine and p-tert-butylbenzoyl
chloride were used as starting materials. The NMR spectrum data of
the obtained Compound (3-16) were as follows:
[0284] .sup.1H-NMR (solvent: DMSO-d6, standard: tetramethylsilane)
.delta. (ppm): 1.35 (18H, s), 7.50-7.60 (7H, m), 7.90-8.00 (4H, m),
7.30 (2H, m), 11.20 (2H, s)
Synthesis of Compound (3-17)
##STR00089##
[0286] Intermediate Compound (3-17-1) was synthesized according to
the method described in Chemistry-A Suropean Journal, 2005, vol.
11, #22 p. 6616-6628, and then Compound (3-17) was synthesized
according to the synthetic process of Compound (3-7). The structure
of the obtained compound was confirmed through MS spectrometry.
Synthesis of Compound (3-18)
[0287] Compound (3-18) was synthesized by a process similar to the
synthetic process of Compound (3-17). The structure of the obtained
compound was confirmed through MS spectrometry.
Synthesis of Compound (C-103)
##STR00090##
[0289] To dimethylacetoamide (300 ml) were added
2-chloro-4,6-diamino-1,3,5-triazine (50 g), morphorine (60 g) and
potassium carbonate (95 g) and the mixture was stirred at
100.degree. C. for 3 hours. The reaction mixture was cooled to a
room temperature and a saline water (1 L) was added thereto. The
mixture was cooled to 10.degree. C. and the precipitated crystal
was separated by filtration. The crystal was washed with water and
acetonitrile and dried to obtain the Intermediate Compound (3-1)
(55 g). The Intermediate Compound (3-1) (40 g), methyl
2-methylbenzoate (64 g), sodium methoxide (55 g) were added to
N-ethylpyrrolidone (400 ml) and the mixture was stirred at
40.degree. C. for 30 minutes. The mixture was cooled to a room
temperature and 1N hydrochloric acid was added thereto. The
precipitated crystal was separated by filtration and washed with
water and dried. The dried crystal was stirred in a mixed solution
of ethyl acetate, methanol and sodium bicarbonate to obtain a
crystal by filtration. The crystal was washed with water and
acetonitrile and dried to obtain Compound (C-103) (60 g).
Synthesis of Compound (C-153)
##STR00091##
[0291] An aqueous solution of methylamine (40%, 60 ml) was added to
2-chloro-4,6-diamino-1,3,5-triazine (20 g) and the mixture was
stirred at 70.degree. C. for 2 hours. The mixture was cooled to a
room temperature and water is added thereto. The crystal was
separated by filtration and washed with isopropanol and hexane and
dried to obtain the Intermediate Compound (43-1). The following
process is the same as that in the synthesis of Compound (C-103)
above to obtain Compound (C-153).
Synthesis of Compound (C-113)
[0292] Methanol (300 ml) and sodium hydroxide (16 g) were added to
2-chloro-4,6-diamino-1,3,5-triazine (27 g) and the mixture was
heated for reflux for 5 hours. The mixture was cooled to a room
temperature and water is added thereto. The crystal was separated
by filtration and washed with water and dried to obtain an
intermediate compound (17 g). The intermediate compound (17 g),
methyl 2-methylbenzoate (38 g), sodium methoxide (33 g) were added
to N-ethylpyrrolidone (200 ml) and the mixture was stirred at
40.degree. C. for 8 hours. The mixture was cooled to a room
temperature and 1N hydrochloric acid, ethyl acetate and hexane were
added thereto. The precipitated crystal was separated by filtration
and recrystallized from isopropanol and dried to obtain Compound
(C-113) (20 g).
Example 301
Production of Protective Film for Polarizer
(Preparation of Cellulose Acylate Solution)
[0293] The following composition was placed into a mixing tank and
stirred to dissolve the components to obtain Cellulose Acylate
Solution 301.
TABLE-US-00006 Composition of Cellulose Acylate Solution 301
Cellulose acylate (degree of substitution with an acetyl group:
100.0 parts by mass 1.6, degree of a propionyl group: 0.8,
polymerization degree: 350) Polycondensated polyester A (weight
average molecular weight: 10.0 parts by mass 1100) Methylene
chloride (first solution) 402.0 parts by mass Ethanol (second
solution) 60.0 parts by mass Polycondensation polyester A
##STR00092##
(Preparation of Matting Agent Solution 302)
[0294] The following composition was placed into a dispersion
machine and stirred to dissolve the components to obtain Matting
Agent Solution 302.
TABLE-US-00007 Composition of Matting Agent Solution 302 Silica
particles (average particle size: 20 nm, 2.0 parts by mass AEROSIL
R972, manufactured by Nippon Aerosil) Methylene chloride (first
solution) 75.0 parts by mass Ethanol (second solution) 12.7 parts
by mass Cellolose Acylate Solution 301 10.3 parts by mass
(Preparation of Solution of Compound Capable of Forming a Hydrogen
Bond 303)
[0295] The following composition was placed into a mixing tank and
stirred with heat to dissolve the components to obtain Solution of
Compound capable of forming a Hydrogen Bond 303.
TABLE-US-00008 Composition of Solution of Compound capable of
forming a Hydrogen Bond 303 Compound capable of forming a hydrogen
bond 10.0 parts by mass (A-35) Methylene chloride (first solution)
67.2 parts by mass Ethanol (second solution) 10.0 parts by mass
Cellulose Acylate Solution 301 12.8 parts by mass
[0296] Matting Agent Solution 302 (1.3 parts by mass) and Solution
of Compound capable of forming a Hydrogen Bond 303 (6.7 parts by
mass) were filtered and mixed with an inline mixer. Cellulose
Acylate Solution 301 (92.0 parts by mass) was added and the
composition was mixed with an inline mixer. The mixed solution was
cast with a band caster and dried at 10.0.degree. C. until the
residual solvent is reduced to less than 40% and then the film was
separated. The separated film was stretched with a tenter at an
atmospheric temperature of 140.degree. C. to the direction
perpendicular to the travelling direction by 30% width expansion.
The stretched film was dried at 140.degree. C. for additional 20
minutes. The produced film has a thickness of 50 microns.
Examples 302 to 313 and Comparative Examples 401 to 405
Production of Protective Film for Polarizer
[0297] The protective films for polarizer of Examples 302 to 313
and Comparative Examples 401 to 405 were produced by the process in
Example 301 except that the degree of substitution of the cellulose
acylate, content of polycondensation polyester A, type and content
of compound capable of forming a hydrogen bond and film thickness
were changed as shown in the following Table 1.
(Evaluation of Optical Properties)
[0298] Cellulose Acylate Films 301 to 313 obtained in Examples 301
to 313 and Cellulose Acylate Films 401 to 405 obtained in the
Comparative Examples 401 to 405 were evaluated in the optical
properties and the change of retardation in humidity change in the
same manner as Example 1.
[0299] These results are shown in Table 7 below.
TABLE-US-00009 TABLE 7 Additive Cellulose acylate Total Nummber
Degree of numnber of of Added substitution Donor and Molecular
Aromatic amount Degree of with Acceptor weight ring [parts by
acetyl propionyl Film Compound (D + A) (M) M/(D + A) structure
ClogP mass] substitution group 401 -- -- -- -- -- -- 0 0.8 1.6 402
U-1 6 412 69 4 7.0 4 0.8 1.6 403 U-4 4 264 66 1 6.3 4 0.8 1.6 404
U-5 6 390 65 0 -1.5 4 0.8 1.6 405 U-6 5 135 27 1 -0.5 4 0.8 1.6 301
A-35 7 362 52 3 4.8 4 0.8 1.6 302 C-116 8 409 51 3 3.0 4 0.8 1.6
303 C-143 8 376 47 3 3.6 4 0.8 1.6 304 D-103 7 258 37 2 1.8 4 0.8
1.6 305 D-104 7 258 37 2 1.8 4 0.8 1.6 306 E-203 6 362 60 3 4.6 4
0.8 1.6 307 E-207 7 377 54 3 4.1 4 0.8 1.6 308 F-111 7 320 46 2 3.5
4 0.8 1.6 309 H-104 6 240 40 2 1.3 4 0.8 1.6 310 A-13 5 209 42 1
3.2 4 0.8 1.6 406 -- -- -- -- -- -- 0 0.2*.sup.) 1.5*.sup.) 407 U-2
6 354 59 4 6.2 2 0.2*.sup.) 1.5*.sup.) 311 A-35 7 362 52 3 4.8 2
0.2*.sup.) 1.5*.sup.) 408 -- -- -- -- -- -- 0 0.1*.sup.) 2.4*.sup.)
409 U-3 6 355 59 4 6.2 5 0.1*.sup.) 2.4*.sup.) 312 A-35 7 362 52 3
4.8 5 0.1*.sup.) 2.4*.sup.) 410 -- -- -- -- -- -- 0 0.1*.sup.)
1.7*.sup.) 411 U-1 6 412 69 4 7.0 3 0.1*.sup.) 1.7*.sup.) 313 A-35
7 362 52 3 6.2 3 0.1*.sup.) 1.7*.sup.) Cellulose acylate Total Film
degree of Thick- propionyl ness Re .DELTA.Re Rth .DELTA.Rth Film
substitution (.mu.m) [nm] [nm] [nm] [nm] Remarks 401 2.4 50 35 12
115 28 comparative example 402 2.4 50 71 10 192 22 comparative
example 403 2.4 50 33 9.3 103 23 comparative example 404 2.4 50 30
11.0 100 26 comparative example 405 2.4 Compound U-6 is insoluble
in the solvent comparative example 301 2.4 50 55 6.2 140 15 example
of the invention 302 2.4 50 54 5.8 140 14 example of the invention
303 2.4 50 57 5.9 143 13 example of the invention 304 2.4 50 53 6.0
138 13 example of the invention 305 2.4 50 50 6.2 137 14 example of
the invention 306 2.4 50 62 5.6 155 14 example of the invention 307
2.4 50 64 5.5 157 13 example of the invention 308 2.4 50 54 6.2 142
14 example of the invention 309 2.4 50 67 5.0 171 13 example of the
invention 310 2.4 50 31 8.0 101 19 example of the invention 406
1.7*.sup.) 60 74 13 252 24 comparative example 407 1.7*.sup.) 60 89
11 282 21 comparative example 311 1.7*.sup.) 60 82 8.0 264 17
example of the invention 408 2.5*.sup.) 50 30 7.0 87 19 comparative
example 409 2.5*.sup.) 50 46 6.0 132 16 comparative example 312
2.5*.sup.) 50 40 3.0 114 8.0 example of the invention 410
1.8*.sup.) 60 67 13 248 23 comparative example 411 1.8*.sup.) 60 93
10 298 21 comparative example 313 1.8*.sup.) 60 72 5.0 272 11
example of the invention *.sup.)The cellulose acylate was prepared
according to the method described in U.S. Pat. Pub. No.
2009/0096962.
##STR00093##
Compound U-5: penta-O-acetyl-.beta.-D-galactopyranose manufactured
by Tokyo Kasei.
##STR00094##
[0300] From the results in the above Table 7, it is known that the
films of the invention, to which the compound capable of forming a
hydrogen bond had been added, were all improved in point of the
humidity dependence of retardation, as compared with the
comparative films to which the compound capable of forming a
hydrogen bond had not been added. In addition, it is also known
that the comparative films of cellulose acylate resin to which any
of the comparative compounds U-1 to U-6 had been added were still
unsatisfactory in point of the humidity dependence improvement.
[0301] While the present invention has been described in detail and
with reference to specific embodiments thereof, it will be apparent
to one skilled in the art that various changes and modifications
can be made therein without departing from the scope thereof.
[0302] The present disclosure relates to the subject matter
contained in Japanese Patent Application No. 225478/2009, filed on
Sep. 29, 2009 and Japanese Patent Application No. 207238/2010,
filed on Sep. 15, 2010, the contents of which are herein
incorporated by reference in their entirety. All the publications
referred to in the present specification are also expressly
incorporated herein by reference in their entirety.
[0303] The foregoing description of preferred embodiments of the
invention has been presented for purposes of illustration and
description, and is not intended to be exhaustive or to limit the
invention to the precise form disclosed. The description was
selected to best explain the principles of the invention and their
practical application to enable others skilled in the art to best
utilize the invention in various embodiments and various
modifications as are suited to the particular use contemplated. It
is intended that the scope of the invention not be limited by the
specification, but be defined claims set forth below.
* * * * *