U.S. patent number 3,615,637 [Application Number 04/882,271] was granted by the patent office on 1971-10-26 for spectrally sensitized photographic silver halide emulsions.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Masanao Hinata, Masao Sawahara, Keisuke Shiba, Nobuo Tsuji.
United States Patent |
3,615,637 |
Shiba , et al. |
October 26, 1971 |
SPECTRALLY SENSITIZED PHOTOGRAPHIC SILVER HALIDE EMULSIONS
Abstract
A supersensitized photographic silver halide emulsion containing
a sensitizing dye represented by the following general formula:
##SPC1## And a condensate of formaldehyde and a polyhydroxybenzene,
which may be substituted or unsubstituted. The emulsion is
supersensitized. The sensitizing dye must contain at least one
quinoline nucleus.
Inventors: |
Shiba; Keisuke (Kanagawa,
JA), Hinata; Masanao (Kanagawa, JA), Tsuji;
Nobuo (Kanagawa, JA), Sawahara; Masao (Kanagawa,
JA) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Kanagawa, JA)
|
Family
ID: |
13952024 |
Appl.
No.: |
04/882,271 |
Filed: |
December 4, 1969 |
Foreign Application Priority Data
|
|
|
|
|
Dec 4, 1968 [JA] |
|
|
43/88768 |
|
Current U.S.
Class: |
430/576; 430/582;
430/586 |
Current CPC
Class: |
C08G
8/08 (20130101); G03C 1/04 (20130101); G03C
1/28 (20130101); C08G 8/30 (20130101); C08G
8/22 (20130101) |
Current International
Class: |
C08G
8/08 (20060101); C08G 8/00 (20060101); G03C
1/08 (20060101); G03C 1/04 (20060101); G03C
1/28 (20060101); G03c 001/28 () |
Field of
Search: |
;96/126,124 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Brown; J. Travis
Claims
What is claimed is:
1. A photographic silver halide emulsion containing at least one
sensitizing dye represented by the following general formula
##SPC7##
wherein Z.sub.1 represents nonmetallic atoms necessary to complete
the 4-quinoline nucleus and Z.sub.2 represents nonmetallic atoms
necessary to complete 5-6 membered heterocyclic rings, R.sub.1 and
R.sub.2 are each a member selected from the class consisting of an
alkyl group having one to five carbon atoms and an alkyl group
substituted by a member selected from the class consisting of
hydroxyl, acetoxy, sulfate, carboxyl carboxy-alkoxyl, sulpho,
hydroxysulpho, alkyoxy-sulphoalkoxy, m represents 1 or 2, x
represents an anion, and p represents 1 or 2, and at least one
condensate of formaldehyde and a member selected from the group
consisting of a substituted polyhydroxybenzene and an unsubstituted
polyhydroxybenzene represented by the following general formulas,
##SPC8##
wherein R.sub.3 and R.sub.4 represents a member selected from the
group consisting of OH, OM, OR.sub.6, NHR.sub.6, NH.sub.2,
N(R.sub.6).sub. 2, NHNH.sub.2, NHNHR.sub.6, wherein R.sub.6 is a
member selected from the group consisting of an alkyl group having
one to eight carbon atoms, an aryl group, and an aralkyl group, and
M is a member selected from metals consisting of an alkali metal
and an alkaline earth metal, R.sub.5 is a member selected from the
group consisting of a hydroxyl group and halogen atoms, n.sup.1 and
n.sup.2 each represents 1, 2 or 3.
2. The photographic silver halide emulsion claimed in claim 1,
wherein said sensitizing dye contains at least one quinoline
nucleus, which may also have substituted thereon groups selected
from the class consisting of halogen atoms, an alkyl group having
one to eight carbon atoms, and alkoxyl group and a hydroxyl group,
and said formalin condensate has 2-10 units as a degree of
polymerization and a molecular weight of 300-800.
3. The photographic silver halide emulsion claimed in claim 1,
wherein the concentration of said sensitizing dye is 0.002-0.2
g/mol. silver halide, and the concentration of said formalin
condensate is 0.1-5.0 g/mol. silver halide.
4. The photographic silver halide emulsion claimed in claim 1,
wherein the concentration ratio of said sensitizing dye to said
formalin concentrate is from 1:5 to 1:500.
5. The photographic silver halide emulsion claimed in claim 1
wherein said silver halide emulsion is a gelatino silver halide
emulsion.
6. The photographic silver halide emulsion claimed in claim 1,
wherein said silver halide is from the group consisting of silver
chloride, silver bromide, silver bromochloride, silver bromoiodide
and silver bromochloroiodide.
7. A photographic silver halide element comprising a support and a
photographic silver halide emulsion layer thereon containing at
least one sensitizing dye represented by the following general
formula: ##SPC9##
wherein Z.sub.1 represents nonmetallic atoms necessary to complete
the 4-quinoline nucleus and Z.sub.2 represents nonmetallic atoms
necessary to complete 5-6 membered heterocyclic rings, R.sub.1 and
R.sub.2 are each a member selected from the class consisting of an
alkyl group having one to five carbon atoms and an alkyl group
substituted by a member selected from the group consisting of
hydroxyl, acetoxyl, sulfate, carboxyl, carboxyalkoxyl, sulpho,
hydroxysulpho, alkyoxy-sulphoalkoxy, m represents 1 or 2, X
represents an anion, and p represents 1 or 2, and at least one
condensate of formaldehyde and a member selected from the group
consisting of a substituted polyhydroxybenzene and an unsubstituted
polyhydroxybenzene represented by the following general formulas,
##SPC10##
wherein R.sub.3 and R.sub.4 each represents a member selected from
the group consisting of OH, OH, OR.sub.6, NHR.sub.6, NH.sub.2,
N(R.sub.6).sub.2, NHNH.sub.2, NHNHR.sub.6 wherein R.sub.6 is a
member selected from the group consisting of an alkyl group having
one to eight carbon atoms, an aryl group and an aralkyl group, and
M is a member selected from the group of metals consisting of an
alkali metal and an alkaline earth metal, R.sub.5 is a member
selected from the consisting of a hydroxyl group and halogen atoms,
n.sup.1 and n.sup.2 each represents 1, 2 or 3.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to photographic silver halide emulsions, and
more particularly, to supersensitized silver halide emulsions.
Description of the Prior Art
It is well known in the technical field of producing photographic
silver halide emulsions that by adding a sensitizing dye to a
photographic silver halide emulsion the light-sensitive wavelength
range is extended and the emulsion is spectrally sensitized.
Further, by adding to the photographic silver halide emulsion
(together with the sensitizing dye) an additive that does not
sensitize the photographic emulsion in the same wavelength range as
that of the sensitizing dye, it is sometimes found that at least a
part of the wavelength range where the dye sensitizes is more
markedly sensitized than when the dye alone is added to the
emulsion. This phenomenon is commonly called "supersensitization"
and other compounds that do not sensitize the photographic emulsion
in the same wavelength range as that of the sensitizing dye are
called "supersensitizers."
SUMMARY OF THE INVENTION
The present invention, essentially, involves the discovery that a
supersensitized photographic silver halide emulsion may be formed
by a combination of certain sensitizing dyes and a condensate of
formaldehyde and a polyhydroxybenzene, which may be substituted or
unsubstituted.
More specifically, the photographic silver halide emulsion must
contain at least one sensitizing dye represented by the following
general formula I: ##SPC2##
wherein Z.sub.1 represents nonmetallic atoms necessary to complete
the 4-quinoline nucleus and Z.sub.2 represents nonmetallic atoms
necessary to complete 5-6 membered heterocyclic rings, R.sub.1 and
R.sub.2 are each a member selected from the class consisting of an
alkyl group having one to five carbon atoms and an alkyl group
substituted by a member selected from the class consisting of
hydroxyl, acetoxy, sulfate, carboxyl carboxyalkoxyl, sulpho,
hydroxysulpho, alkoxy-sulphoalkoxy, m represents 1 or 2, X
represents an anion, and p represents 1 or 2, and at least one
condensate of formaldehyde and a member selected from the group
consisting of a substituted polyhydroxybenzene and an unsubstituted
polyhydroxybenzene represented by the following general formulas,
##SPC3##
Wherein R.sub.3 and R.sub.4 each represents a member selected from
the group consisting of OH, OM, OR.sub.6, NHR.sub.6, NH.sub.2,
N(R.sub.6).sub.2, NHNH.sub.2, NHNHR.sub.6, wherein R.sub.6 is a
member selected from the group consisting of an alkyl group having
one-eight carbon atoms, an aryl group and an aralkyl group, and M
is a member selected from metals consisting of an alkali metal and
an alkaline earth metal, R.sub.5 is a member selected from the
group consisting of a hydroxyl group and halogen atoms, n.sup.1 and
n.sup.2 each represents 1, 2 or 3.
It is an object of the present invention to provide a
supersensitized photographic silver halide emulsion.
It is a further object to provide a spectrally sensitized
photographic silver halide emulsion.
These and other objects will become clear upon a reading of the
following detailed description of the preferred embodiments of the
invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The inventors have found that by incorporating in a photographic
silver halide emulsion the sensitizing dye shown in following
general formula (1), together with the novolak-type condensate of a
substituted or an unsubstituted polyhydroxybenzene and
formaldehyde, supersensitization can be obtained. Here the term
polyhydroxybenzene means one having one to three hydroxy groups on
the benzene nucleus. The novalak-type condensate of a substituted
or an unsubstituted polyhydroxybenzene and formaldehyde is
hereinafter called simply a "formalin condensate."
General formula (1) is: ##SPC4##
wherein Z.sub.1 represents a nonmetallic atom group necessary to
complete the 4-quinoline nucleus; Z.sub.2 represents a nonmetallic
atom necessary to complete a 5-6 membered heterocyclic ring;
R.sub.1 and R.sub.2 represent a substituted or an unsubstituted
alkyl group; m represents 1 or 2, X represents an anion; p
represents 1 or 2, p being 1 when the dye forms an internal
salt.
The 4-quinoline nucleus containing Z.sub.1 may also contain such
substituted groups as halogen atom, an alkyl group, an alkoxyl
group, a hydroxyl group, etc., Z.sub.2 represents nonmetallic
groups necessary for completing heterocyclic rings such as e.g., 4
-quinoline nucleus, 2 -quinoline nucleus, benzothiazole nucleus,
naphthothiazole nucleus, benzoselenazole nucleus, naphthoselenazole
nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazole
nucleus, oxazole nucleus, benzoimidazole nucleus, 3,3
-dialkylindolenine nucleus, etc., R.sub.1 and R.sub.2 each
represents a lower alkyl group (e.g., methyl group, ethyl group,
propyl group, etc.) or substituted alkyl group such as a
.beta.-hydroxyethyl group, .beta.-acetoxyethyl group, ethyl sulfate
group (-C.sub.2 H.sub.4 SO.sub.4 H), carboxymethyl group,
.beta.-carboxyethyl group, .gamma.-carboxypropyl group,
2-(2-carboxyethoxy)ethyl group, .beta.-sulphoethyl group,
.gamma.-sulphopropyl group, 2 -hydroxy- 1 -sulphopropyl group, 3
-methyoxy- 2-(3 -sulphopropoxyl)propyl group, etc. The basic
chemical structural feature of this sensitizing dye is that it
contains at least one quinoline nucleus.
The substituted or unsubstituted polyhydroxybenzene used in the
present invention is shown by the following general formulas:
##SPC5##
wherein R.sub.3 and R.sub.4 each represents OH, OM, OR.sub.6,
NH.sub.2, N(R.sub.6).sub.2, NHNH.sub.2, NHR.sub.6, or NHNHR.sub.6
(where R.sub.6 represents an alkyl group having one to eight carbon
atoms, an aryl group, or an aralkyl group, and M represents an
alkali metal or an alkaline earth metal), R.sub.5 represents a
hydroxyl group or halogen group, and n.sup.1 and n.sup.2 each
represents 1, 2, or 3.
Typical examples of compounds shown by the above general formulas
are p-dihydroxybenzene, o-dihydroxybenzene, p-hydroxybenzoic acid,
p-hydroxybenzenesulphonic acid, m-hydroxybenzoic acid,
m-hydroxybenzenesulphonic acid, .alpha.-resorcinic acid,
.beta.-resorcinic acid, .gamma.-resorcinic acid, 3,5
-dihydroxybenzenesulphonic acid, 2,4 -dihydroxybenzenesulphonic
acid, 2,6 -dihydroxybenzenesulphonic acid, 2,5 -dihydroxybenzoic
acid, 3,5-dihydroxybenzoic acid, 2,5-hydroxybenzenesulphonic acid,
pyrogallol carboxylic acid (5 ), pyrogallol carboxylic acid (4),
pyrogallol sulfonic acid (5), pyrogallol sulfonic acid (4) and
their alkali metal salts (Li, Na, K, etc.), and their alkaline
earth metal salts (Mg, Ca, etc.). Further examples of materials
effectively used in the present invention are the amides or
hydrazides of the above-mentioned carboxylic acids or sulfonic
acids, and amide compounds or hydrazide compounds of these N-alkyl
(one to eight carbon atoms) or N-aralkyl or N-allyl derivatives.
The esters of the above-mentioned carboxylic acids or sulfonic
acids can also be effectively employed in this invention.
The condensate of the above-mentioned substituted or unsubstituted
polyhydroxybenzene and formaldehyde may be prepared by any
conventional method for forming a novolak-type phenol-formaldehyde
resin. While the preparation thereof is not particularly critical,
such a material is generally prepared as follows. The
polysubstituted hydroxybenzene is dispersed in water, and after
adding concentrated hydrochloric acid and 37 percent formalin, the
dispersion is stirred for 30 to 60 minutes at 100.degree. C.
Thereafter, if necessary, hydrochloric acid is added, followed by
the continuation of heating and stirring. After the reaction is
finished, the product is poured into cold water and the precipitate
is collected and purified to provide the condensate. Another
example will now be described in more detail. For example, 415
parts of p-hydroxy-benzoic acid is dispersed in 1,000 parts of
water with vigorous stirring and 25 parts of 35 percent (or
greater) concentrated hydrochloric acid and 245 parts of 37 percent
formalin are added to the dispersion. The reaction mixture is then
stirred for 30 minutes at 100.degree. C. and, after the addition of
20 parts of concentrated hydrochloric acid, the system is reacted
for a further 30 minutes.
At the end of the reaction, 20 parts of concentrated hydrochloric
acid is added to the reaction product and the system is stirred,
whereby the reaction solution becomes turbid and white. After
stirring for about 90 minutes, stirring is stopped and the reaction
mixture is poured into 3,000 parts of cold water, with stirring.
The product thus precipitated is separated by filtration,
redissolved in 1,000 parts of methanol while the product is not yet
dried, and then reprecipitated by adding water. The product is
recovered by filtration and dried to provide the desired
condensate. In the cases where other substituted or unsubstituted
polyhydroxybenzenes are employed in place of the above-mentioned
p-hydroxybenzoic acids, the above-mentioned method or a slightly
modified method can be applied to easily obtain the condensate. The
condensate obtained by the above-mentioned method has, like the
common novolak-resin, about 2-10 units in a condensation unit
(degree of polymerization).
A condensate having 2-10 units in its degree of polymerization is
effective in the present invention, but a condensate having 2-5
units in its degree of polymerization and having a molecular weight
of 300-800 is particularly desirable.
When a formalin condensate of the present invention is added to a
silver halide emulsion containing the sensitizing dye of formula (1
), excellent supersensitization can be obtained and, moreover, the
formation of fog can be remarkably reduced compared with the case
where the sensitizing dye alone is added to the emulsion. Some of
the sensitizing dyes of formula (1 ), when incorporated in
photographic light-sensitive materials, have the drawback that
their sensitivity is lowered during storage, but such a lowering of
sensitivity during storage can be remarkably prevented by
incorporating the dye in the emulsion together with the formalin
condensate in accordance with the present invention.
The concentration of the sensitizing dye of the present invention
in the silver halide emulsion is preferably 0.002-0.2 g./mol.
silver halide, and the concentration of the formalin condensate in
the said emulsion is preferably 0.1-5.0 g./mol. silver halide. The
most effective concentration ratio of the sensitizing dye to the
formalin condensate is preferably from 1:5 to 1:500.
The sensitizing dye may be added into the emulsion by any suitable
method known in this field. The formalin condensate may be
incorporated in the silver halide emulsion as a solution thereof in
water or in an organic solvent such as methanol or ethanol. It is
convenient to incorporate the sensitizing dye and the formalin
condensate into the emulsion before coating.
The sensitizing dye may be added into the emulsion either before or
after the addition of the formalin condensate, or a mixture of the
sensitizing dye and the formalin condensate may be added into the
emulsion. Further, they may be added into the emulsion not only
before coating but also during ripening of the emulsion after
washing.
In the present emulsion, gelatin is generally used as a binder for
the silver halide emulsion, but other binders such as resinuous
material or cellulose derivatives which do not have a bad influence
on the photographic light sensitive materials may be used.
The photographic emulsion used in this invention may be a
gelatino-silver halide such as a gelatino silver-chloride,
-bromide, -bromoiodide, -bromochloride or -bromochloroiodide.
The silver halide emulsion used in this invention may further
contain the normal state of the art additives such as a chemical
sensitizer, an antifoggant, a stabilizer, a hardening agent, a
wetting agent, a plasticizer, a developing accelerator, a toner, a
fluorescent whitening agent, an antiairfoggant, a coupler, etc. The
silver halide emulsion may be applied by any conventional method to
a suitable support such as a glass plate, a cellulose derivative
film, a synthetic film or a baryta paper.
The sensitizing dyes of the formula (I) employed in the present
invention are described below, but it should be understood that
they are not limited to the following examples. ##SPC6##
The examples of the present invention are concretely described
below, but it should be noted that the present invention is not
limited to these examples.
EXAMPLES
To different portions of silver halide emulsions from the same
batch were added (1) only a sensitizing dye shown by general
formula (I); and (2) a combination of a sensitizing dye shown by
general formula (I) and a formalin condensate. Each then was
applied to a cellulose acetate base. If the pH was lowered by the
addition of the formalin condensate into the emulsion, the pH was
adjusted by the addition of an alkali. After drying, the film thus
coated was exposed through a Fuji No. 7 Filter (made by Fuji Photo
Film Co. Ltd., transmitting light having a wavelength longer than
590 millimicrons) and then developed.
The sensitivity of the film is shown by the reciprocal of the
exposure necessary to give fog +0.1 in optical density. The
sensitivity in the case of incorporating only the sensitizing dye
in the emulsion is defined to be 100, and the sensitivity in the
case of incorporating the formalin condensate together with the
sensitizing dye in the emulsion is shown by a comparison with the
defined sensitivity.
In the case of incorporating only the novolak-type condensate of
substituted or unsubstituted polyhydroxybenzene and formaldehyde in
the emulsion, no sensitizing action on the emulsion (or a very low
sensitizing action) was produced, so that the numerical value is
not shown. The emulsions used in the comparative formulas were from
the same batch, but in other formulas various emulsions from
different batches were used. The results are shown in table 1, in
which a silver chlorobromide emulsion from the same batch was used
in examples 1 and 2; a silver bromo-iodide emulsion from the same
batch was used in examples 3-10; and a silver chloro-bromide
emulsion from the same batch was used in examples 11-18. Further,
the photographic light sensitive elements prepared as in examples
1-2 and 11-18 were developed for 2 minutes at 20.degree. C. in a
developer having the composition shown in table 2, and those in
examples 3-10 were developed for 4 minutes at 20.degree. C. in a
developer having the composition shown in table 3.
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TABLE 1
Additives (mg./mol silver halide) Sensitivity Fog
__________________________________________________________________________
1 (a) I-8 (35) 100 0.16 (b) I- 8 (35)+ Condensation product of
.beta.-resorcinic acid and formalin (350) 120 0.06 (c) I-8 (35 )+
Condensation product of .beta.-resorcinic acid and formalin (1480)
135 0.06 (d) I-8 (35)+ Condensation product of 4-Hydroxybenzoic
acid hydra- zide and formaldehyde C350) 120 0.08 (e) I-8 (35)+
Condensation product of 3,5-Dihydroxybenzoic acid hydrazide and
formaldehyde (28) 120 0.11 (f) I-8 (35)+ Condensation product of
p-Chlorophenol and formalde- hyde (700) 190 0.08 (g) I-8 (35)+
Condensation product of Sodium hydroxybenzene- sulfonic acid and
formalde- hyde (350) 120 0.12 (h) I-8 (35)+ Condensation product of
p-Hydroxybenzoic acid and formaldehyde 130 0.06 (i) I-8
(35)+Condensation product of O-Hydroxybenzoic acid and formaldehyde
(1400) 250 0.08 2 (j) I-6 (40) 100 0.08 (k) I-6 (40)+ Condensation
product of m-Hydroxybenzoic acid and formaldehyde (2800) 180 0.06 3
(j) I-7 (39) 100 0.07 (m) I-7 (39)+ Condensation product of
o-Hydroxybenzoic acid and formaldehyde (2800) 130 0.04 4(n) I-4
(78) 100 0.06 (o) I-4 (78)+ Condensation product of
o-Hydroxybenzoic acid and formaldehyde (1400) 140 0.05 5 (p) I-2
(72) 100 0.06 (q) I-2 (72)+ Condensation product of
o-Hydroxybenzoic acid and formaldehyde 150 0.04 6 (r) I-3 (38) 100
0.06 (s) I-3 (38)+ Condensation product of o-Hydroxybenzoic acid
and formaldehyde (2800) 130 0.06 7 (t) I-5 (34) 100 0.06 (u) I-5
(34)+ Condensation product of Hydroquinone and formalde- hyde
(1400) 290 0.06 8 (v) I-1 (70) 100 0.06 (w) I-1 (70)+ Condensation
product of o-Hydroxybenzoic acid and formaldehyde (70) 120 0.06 9
(x) I-8 (70) 100 0.11 (y) I-8 (70)+ Condensation product of Gallic
acid and formaldehyde (2800) 150 0.06 10 (a') I-9 (42) 100 0.04
(b') I-9 (42)+ Condensation product of m-Hydroxybenzoic acid and
formaldehyde (2800) 190 0.04 11 (c') I-10 (84) 100 0.04 (d') I-10
(84)+ Condensation product of m-Hydroxybenzoic acid and
formaldehyde (5600 ) 120 0.04 12 (e.alpha.) I-11 (41) 100 0.04 (f')
I-11 (41)+ Condensation product of m-Hydroxybenzoic acid and
formaldehyde (2800) 130 0.04 13 (g') I-12 (41) 100 0.04 (h'I-12
(41)+ Condensation product of m-Hydroxybenzoic acid and
formaldehyde (2800) 140 0.04 14 (i') I-13 (45) 100 0.04 (j') I-13
(45)+ Condensation product of m-Hydroxybenzoic acid and
formaldehyde (1400) 200 0.04 15 (K') I-14 (40) 100 0.04 (l') I-14
(40 )+Condensation product of o-Hydroxybenzoic acid and
formaldehyde (2800) 170 0.07 16 (m') I-15 (38) 170 0.07 (n') I-15
(38)+ Condensation product of o-HYdroxybenzoic acid and
formaldehyde (2800) 210 0.04 17 (o') I-16 (37) 100 0.09 (p') I-16
(37 )+Condensation product of o-Hydroxybenzoic acid and
formaldehyde (2800) 250 0.04 18) (q') I-17 (35) 100 0.06 (r') I-17
(35)+ Condensation product of o-Hydroxybenzoic acid and
formaldehyde (2800) 170 0.04
__________________________________________________________________________
Of course, the numerals in parentheses following the material
identification are the amount in mg/mole silver halide.
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TABLE 2
N-Methyl-p-aminophenol sulfate 3.1 g. Sodium sulfite 45.0 g.
Hydroquinone 12.0 g. Sodium carbonate (anhydrous) 67.5 g. Potassium
bromide 1.9 g. Water, up to 1.01
__________________________________________________________________________
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TABLE 3
N-Methyl-p-aminophenol sulfate 2.2 g. Sodium sulfite 96.0 g.
Hydroquinone 8.8 g. Sodium carbonate 48.0 g. Potassium bromide 5.0
g. Water, up to 1.01
__________________________________________________________________________
The term "lower alkyl" in this specification means methyl group,
ethyl group, propyl group and butyl group. For R.sub.6, an aralkyl
group can have 1-8 carbon atoms. The condensation reaction is
further described in "Preparative Methods of Polymer Chemesitry"
published by John Wiley and Sons, Inc. in 1961, W. R. Sorenson and
P. W. Campbell. Finally, the condensate reaction of the substituted
or unsubstituted polyhydroxybenzene and formaldehyde is always
carried out in acidic range.
* * * * *