DE2163811A1 - Process for making cyan images - Google Patents

Description

Act: 47 982

Applicant: Konishiroku Photo Industry Co., Ltd., 1-10, 3-Chome, Nihonbashi-Muro-machi, Chuo-ku, Tokyo , Japan

Process for making cyan images

The present invention relates to a method for producing cyan images by exposing a color photographic Recording material and development. More specifically, the present invention relates to a method Production of cyan images, where a so-called two-equivalent cyan dye is used as a color-forming coupler.

Photographic processes are generally known in which a photographic recording material containing couplers exposed and then developed with a developer which is an aromatic primary amine type developing agent contains. A color image is thereby generated. Of those in this one Couplers used in the process are the cyan couplers obtained by coupling with the oxidation product of a developing agent Type of aromatic primary amine an indoaniline dye form phenol or Ί-faphthol derivatives. If the 4 position these phenol or 1-naphthol derivatives are not substituted, it takes four molecules of silver halide to form one molecule of dye. Therefore these couplers are four-

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called equivalent coupler.

It is also known that when the hydrogen atom in the 4-position has been substituted by a halogen atom such as chlorine, the coupler is the same dye as in the case of Can form four-equivalent couplers. In this case, the halogen atom is peeled off in the course of color development, and 1 mole kül dye can consist of 2 molecules of the developed silver halide are formed. Accordingly, these couplers are called two-equivalent couplers.

The two-equivalent couplers are superior to the four-equivalent couplers in the following points:

1. The two-equivalent couplers have a higher coupling reactive pretended to be the well-known four-equivalent coupler.

2. The amount required to produce a certain amount of dye -: '. -Large amount of silver halide can be half that Amount required in the case of the four-equivalent coupler so that the amount of silver halide can be reduced.

5 · The emulsion layer can be made thinner so that . the resulting color image has improved resolution and sharpness.

4. In the case of multilayer photographic recording materials, the light penetrates into the lower layers improved, so that the sensitivity of the photographic material is improved.

Accordingly, the use of the two-equivalent coupler leads too many advantages in the formation of a color image in a multilayer light-sensitive color photographic recording material.

The above-mentioned excellent properties are particularly pronounced when the hydrogen is in the 4-position of the cyan coupler (hydrogen in the coupler position) substituted has been replaced by an In <3azolyl group such as

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-3-

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CH

. This substituent has the property

that nourishing the color development is released * • The present "invention is therefore based on a method of manufacture of cyan images by exposing a color photographic Recording material and development. The method according to the invention is characterized in that a photosensitive · Color photographic recording material with at least one silver halide emulsion layer containing a compound the general formula

wherein Afiir has a cyan image forming coupler moiety an oic-naphthol or phenol nucleus, the group

is bonded in the p-position to the hydroxyl group of A and Z represents an atomic grouping necessary for the formation of an indazolyl group,

imagewise exposed and color developed, or that a light-sensitive, color photographic recording material imagewise exposed and color-developed using a color developer which is a compound of the above general Formula I contains. This creates a cyan image that corresponds to the silver image formed in the photographic recording material cht.

Some two-equivalent couplers are prone to fogging and they have a property of inhibiting development. The two equivalent couplers according to the present invention however, they are colorless and hardly form a color haze. In addition, the cyan dyes have the result of color development the cyan couplers used according to the invention are obtained, a high light fastness, moisture fastness and V / poor

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resistance. In addition, the absorption is sharp and they "possess" an extremely beneficial shade for earbuds. Certain couplers used in accordance with the invention can be used as So-called DIR (development inhibitor-releasing type) couplers act, which release a substance that at the time of the ilarb development inhibits development.

Thus, the couplers used in the present invention are two-equivalent couplers represented by the following formula

T "- -GH.

Ve?

• ν .. -

it "./

wherein A is a residue of a gyan image-forming coupler having a pt-naphthol or phenol nucleus from which the Hydrogen p-to the hydroxyl group has been removed; and-Z is an atomic grouping that leads to the formation an indazolyl group is required.

Typical examples of couplers made in accordance with the present invention can be used are named below. The couplers useful in accordance with the invention are Examples limited. ------

(1)

* ■ \ 3F ~ ■

1-Η7ατοχ7Μ2 ^ 7) -Ν- (6 (2,4-di-tertamylphenoxy ^ utylj-2-naphthamxd

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(2) 1-Hydroxy-W2 '- (^ - chlorofincrlyl)) -N- (n ~ dodecyl) -2-naphthamide-

OH

, -CONHC ₁₂ H

N CH

Cl

(3) l-Hydroxy-4- (2 '- (6-nitroindazolyl)) -Ν- (δ di-tert-amy! phenoxy) butyl) -2-naphthamide

OH

N CH

NO

. 1-Hydroxy-4- (2 '- (6-aminoindaz οIy 1)) -N- (δ Γ2 4-di-tert-amylphenoxy) -butyl) -2-naphthamide *

OH

N CH

-6-

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(5)! -Hydroxy - ^ - (2 · - (6-acetaminoindazolyl)) -N- (δ (2,4-di-t er t -amy! Phenoxy) -butyl) -2-naphthamide '

OH

N- CH

NHCOCH,

(6) 1-Hydroxy-4- (2 '- (6-chloro / indazolyl)) - 4 ¹ - (4-tert-buty! Phenoxy) -2-naphthanilide

OH

noS

N CH

Cl

(7) l-Hydroxy-4- (2 '- (6-nitroindazolyl)) - N- (ndodecyl) -2-naphthamide'

OH

N CH

NO,

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(8) 1-Hydr pxy-4-- (2 - (5-chloro * indazolyl)) -N- (2 - ethylhexyl) naphthamide

(9) 1-Hydroxy-4- (2'-indazolyl) - ^ - '- (4-tert- "butylphenoxy ) -2-naphthanilide

N CH

(10) 1-Hydroxy-4- (2 V-indazolyD-N-Cn-octadecyl) -2-naphthaitiide

This connection can easily ... be established by the fact that from a corresponding coupler of 1-naphthol type and 2-aminobenzyl alcohol a colored cyano compound produced and

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these in 50 $ HpSD. is heated

The establishment of the connections is based on the following Synthesis "examples explained.

Production example 1

Synthesis of 1-hydroxy-4- (2'-indazolyI) -E- C ^ - (2,4-ai-tert-amino phenoxy) - "butyl} -2-naphthamide (coupler ITr. 1) .:

a) Synthesis of T-Hydroxy -2- (2-hydroxy methy Ipheny lazo) -N- (ί - (2, di-tert-amy! phenoxy) -buty 3 ^ -2-na ph thamid:

In a solution of 20 g of 2-aminobenzyl alcohol in 250 ml 10biger hydrochloric acid at 0 'up to 5 ⁰ C under stirring, a solution of 10.5 g of sodium nitrite in 75 ml water is added dropwise, to prepare a solution of a diazonium salt wu This solution:. De at 20 to 25 ^° C. with stirring into a solution of 60 g of 1-hydroxy-N-Ci (2,4-di-tert-amy! Phenoxy) butyl) -2-naphthamide in 1.2 1 of pyridine, and the mixture of solutions was stirred at this temperature for 2 hours. The reaction mixture was poured into an aqueous dilute hydrochloric acid and then extracted with ethyl acetate. Then, ethyl acetate was removed by distillation, and the residue was recrystallized from a mixture of ethyl acetate and η-hexane to give the desired compound. F * 122-125 ⁰ C, yield 65 g

b) Synthesis of 1-hydroxy-4- (2'-indazolyl) -N- $ - (2,4-di-tertamy ! phenoxy) -bu tylj -2-naphthamide:

50 g of 1-hydroxy-4- (2-hydroxymethylphenylazo) -N- (A - (2,4-di-tertamylphenoxy) -butyl) -2-naphthamide, which was obtained according to a), were added to 800 ml of 50 g Sulfuric acid was added, and the resulting mixture was ^{heated on a water bath (80-90 0} C) for 2 hours with stirring. The reaction mixture was then poured into ice water and extracted with ethyl acetate. Then the ethyl acetate was removed by distillation and the residue was recrystallized from alcohol, whereby the desired compound was obtained in a yield of 32 g with a melting point of 225-227 ° C.

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Elemental analysis:

calculated 71 .86 6th ... 96 6th .45 found 71 .61 7th .15 6th .12

Production example 2

Synthesis of 1-Hydroxy-4-C2 ¹ - (5-chloroindazolyl)} -N- (n-dodecyl) -2-naphthamide (Coupler No. 2) t

a) Synthesis of 1-hydroxy-4- (2-hydroxymethyl-r4-chlorophenylazo) -N- (n-doäecyl) -2-naphthamide:

A solution of 8 g of sodium nitrate in 50 ml of water was added to a solution of 16 g of 2-amino-5-chlorobenzyl alcohol in 250 ml of hydrochloric acid with stirring at "0" to 5 ° C. This solution was stirred at ⁰ 15-2o C in a solution of 55 g of 1-hydroxy-F- (n-dodecyl) -2-naphthamide in 2 1 of pyridine dripped, and the mixture solution was then stirred for 2 hours at room temperature. The reaction mixture was poured into a dilute aqueous hydrochloric acid and extracted with ethyl acetate. Then, the ethyl acetate was removed by distillation and the residue was recrystallized from methanol to give the desired compound. Yield 50 g, P. 137-138 ⁰ C.

b) Synthesis of 1-hydroxy-4- (2 '- (S-chloroindazolyl)) -F- (n-dodecyl) -2-naphthamide: ' - 40 g of 1-hydroxy-4 ~ (2 '^ hydroxymethyl ~ 4-chlorophenylazo) -: N- (n-do- 'decyl) -2-naphthamide, which according to a). was added to 600 ml of 50% sulfuric acid, and the resulting mixture was heated on a water bath for 2.5 hours with stirring. The reaction mixture was then poured into ice water and extracted with ethyl acetate. The ethyl acetate was removed by distillation and the residue was recrystallized from alcohol to give the desired compound in a yield of 23 g.

Elemental analysis:

CH %) H .17 N (Si) calculated 71 • 19th 7th .14 8.3-1 found 71 .07 7th 8.56

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Production example 3:

Synthesis of 1-Hydroxy-4-C2 '- (6-aminoindazolyl) ^ -N-Cp (2,4-di-tert-aminophenoxy) -butyl) -2-naphthamide (Coupler No. 4); A solution of 20 g of 1-hydroxy-4- (2 '- (δ-nitroimidazolyl)) -N- (2,4-di-tert-amylphenoxy) butyl) -2-naphthamide in 500 ml of 90% acetic acid was made heated with stirring to 90-100 ⁰ C. 7.5 g of iron powder were added to this solution at an elevated temperature, and the resulting mixture was stirred as it is for 30 minutes. After the reaction mixture was cooled, insoluble parts were filtered off, and the filtrate was poured into water / water, whereby crystals separated out. The crystals were collected by filtration and then recrystallized from methanol, whereby the desired compound was obtained in a yield of 12 g.

Elemental analysis:

0 (56) H (56) N W. calculated 75.21 7-64. ' 9 .23 found 75-46 7.38 9 .20

Compound No. 5 is prepared by acylating compound No. obtained by methods known per se. Other compounds are obtained by the same procedures as described in FIGS. above production examples have been described.

The couplers obtained in this way can be converted into light-sensitive, color- ' photographic recording materials in per se known Way to be incorporated. For example, one or two or more of these couplers can be used in a high-boiling solvent with a boiling point above 175 ° C, such as tricresylphosph or dibutylphthalate or in a low-boiling solvent such as butyl acetate or butyl propionate (either alone or in the form of a Geraisches) can be dissolved, and the obtained Solution is mixed with an aqueous gelatin solution containing a surfactant. Then by means of a A high-speed rotary mixer or a colloid mill produces a coupler dispersion. This dispersion is then

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followed immediately into a photographic silver halide emulsion given, which is then applied to a carrier and dried. Alternatively, the mentioned Dispersion initially solidified, finely cut, dated Low-boiling solvent freed by washing with water or in a similar manner and turned into a photographic Emulsion are given, which is then applied to a carrier and dried. In this case the amount is of the coupler to be added to the photographic emulsion is preferred 10 to 300 grams per mole of silver halide. However, it can be changed depending on the specific application of the photographic material obtained will. -.

The photographic ones used in accordance with the present invention Emulsions can be made using various silver halites such as silver chloride, silver iodobromide and Silver chlorobromide. These emulsions can be chemical sensitizers, e.g. sulfur sensitizers, natural sensitizers as found in gelatin, reductive sensitizers and precious metal salts. In addition, the emulsions can contain conventional photographic additives, such as Antifoggants, stabilizers, anti-color fogging agents, anti-irradiation agents, improving physical properties high polymer additives, hardeners and coating auxiliaries. You can also use known carbocyanine dye e, merocyanain paraffin, etc., as well as optical sensitizers for the emulsion included.

The invention is further developed with the aid of the following examples explained. .

example 1

2.0 g of coupler no. 1 were dissolved in a solvent mixture of 2 ml of dibutyl phthalate and 6 ml of ethyl acetate. The solution obtained was mixed with 40 ml of a 6% aqueous gelatin solution and 6 ml of a 5% aqueous solution of alkanol B '-1P-

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(manufactured by Du Pont) and the mixed solution was made using a colloid mill to form a Coupler dispersion subjected to the usual treatment by the protected dispersion method. This dispersion became one Silver iodia bromide emulsion containing 5 g of silver halide particles given. Then, the emulsion was coated on a triacetate support and dried to obtain a sample became.

For comparison, a control sample in the same V was prepared / else as described above, with an identical in structure of the coupler has been used with the only deviation i that it no indazolyl-substituent, such as the coupler no. 1 "

The samples obtained in this way were each exposed in the usual way and developed for 10 minutes at 24 ^° C. with a developer of the following composition:

anhydrous sodium sulfite 2.0 g

N-ethyl-N-ß-methanesulfonamiäoäthyl-3-methyl-4-aminoanilinsulfat 5th floor

Sodium carbonate (monohydrate) 50.Ό g Sodium bromide 0.9 g

Sodium hydroxide 4 * 0 g

Sodium hexamethaphosphate 0.5g '

Benzyl alcohol 4.0 ml

pure water up to 1,000 ml

It was then bleached and fixed in the usual way, with the results compiled in Table 1 were obtained:

Table 1

Coupler

Λ-max (mp)

Coupler No. 1 according to the invention

Control coupler 69Ο

D-max

3-5

2.8

relative sensitivity veil gamma

130

100

0.09

0.11

2.2

2.0

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From the results compiled in Table 1 it can be seen that that the sample containing coupler No. 1 had improved relative sensitivity in spite of less fog, has better gamma and D-max than the sample, which contains the control coupler. Coupler No. 1 according to the invention is thus considerably superior to an identical coupler which does not contain the indazolyl substituent.

Samples were also prepared, each using the for example 5, 9 and 10 instead of the No. 1 coupler, respectively. These samples have one too lower emulsion haze and an improved relative Sensitivity, improved gamma and D-max than the sample, which contains the control coupler.

Example 2

Samples were prepared in the manner described in Example 1, using 2.0 g of coupler no. 10 and wherein the amount of silver iodobromide contained in the emulsion was 1.25 g, 2.5 g and 5.0 g, respectively.

For comparison, control samples were prepared in the same way, a coupler which was identical to coupler No. 10 with the only difference that it was not the Indazolyl Suhstituent contained, in the same amounts as above was used.

These samples were exposed and then exposed in the same manner as described in Example 1, the results summarized in Table 2 were obtained.

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Coupler

Amount of silver halide

(G)

Coupler # 10
according to the invention

Control coupler

2.5

1.25

2.5

1.25

- 14 -. Table 2

veil

0.13 0.10 0.08 0.11 0.09 0.07

relative sensitivity

gamma

135
110

107

100

74

54

2.3 2.1 2.0 2.0 1 .8 1.5

From Table 2 it can be seen that even if the SiI ||, the excess halide amount is reduced to 1/4, the sample containing the Coupler No. 10 according to the invention contains significantly better properties than the control sample containing the control coupler contains. The use of the coupler according to the present invention thus results in an extremely large one technical effect in terms of the possibility of using a considerably smaller amount of silver halide ^.

Example 3 '

A silver halide emulsion containing 5 g of silver chlorobromide, to which 2.0 g of Coupler No. 10 had been added was coated on a support to prepare a sample. This sample was exposed and developed in the usual way *. The developer used was identical to the developer used in Example 1 with the only difference - that as Developing agent N-methyl-p-phenylenediamine hydrochloride is used became. After the development, the sample was sufficiently washed with water, dried and then given in Table 3 Subject to tests. The results compiled in Table 3 were obtained.

For comparison, a control sample was used in the same way as described above with the modification that the therein coupler used had no indazolyl substitution, im but was otherwise identical in structure to coupler No. 10 according to the invention. This sample was made in the same way

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treated like the other samples. The result achieved is also shown in Table 3.

Treatment conditions:

Lightfastness: carbon arc lamp, 5, O ⁰ C, 1.6. h, 32 h.

Moisture fastness and heat resistance-Iceit:

RH $ 80, 77 ° C, 7 days, 14 days.

Table 3 ■ Coupler Lightfastness
(Augb 1 ei chve r
nis) Moisture fastness and
Heat resistance (Aus
bleach ratio) • 16 h 32 h. 7 days 14 days Coupler No. 10
Control coupler 3 7
a 20 5 11
9 23

Fading behavior Fading. (50) after treatment of the

Part »which initially had a density of 1.0.

From the results compiled in Table 3 it can be seen that that the sample containing the coupler according to the invention has a significantly better lightfastness, moisturefastness and V / heat resistance than the control sample which has the Contains control coupler.

Example 4

Sample A was made as follows:,, A mixture of 0.75 g of coupler no. 1, 0.75 g of an identical coupler, but which does not have the indazolyl substitution had, and 0.5 g of the color coupler (1-hydroxy-4- (2'-acetylphenylazo) -N (i- (2,4-di-tert-amylphenoxy) -butyl) -2-naphthamide), which corresponds in terms of the core to coupler No. 1 according to the invention, were in a solution - ■ medium mixture of 2 ml tricresyl phosphate and 7 ml ethyl acetate ■ solved. The resulting solution was poured into 40 ml of a 5? ■ aqueous G-elatin solution containing 4 ml of an aqueous solution

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Sodium n-dodecylbenzenesulfonate solution dispersed. This dispersion became a red sensitive photographic emulsion given containing 5 g of silver iodobromide. This then became applied to a cellulose triacetate carrier in a thickness of 5 microns and dried.

For comparison, Sample B was made in the same manner as described above produced, but instead of the coupler lir. 1 According to the invention, 0.6 g of a coupler were used which had the same structure as the coupler Ur. 1 according to the invention but did not have the indazolyl substitution.

Samples A and B were subjected to the same exposure and development as in Example .1, with those in the table 4 results compiled were obtained.

A.
B. veil Table 4 gamma D -max 0.10
0.11 rel. Sensitive
speed 1.43
1.44 3.15-
2.88 sample
sample 115
100

From the results compiled in Table 4 it is ■ it is evident that even when the couplers according to the invention are used in admixture with couplers, they are not. fall within the scope of the present invention are excellent Effects can be obtained. Thus, when the coupler of the present invention is mixed with coupler! used that are not within the scope of the present invention fall, the photographic recording material obtained may in terms of sensitivity, D-max and the like ' Properties can be controlled simply by the The mixing ratio of the couplers is changed without changing the size or amount of the silver halide particles.

Example 5

A sample A was prepared by using a coupler mixture ·

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from 0.20 g of coupler No. 3 according to the invention and 1.50 g a coupler having the same structure as coupler No. 3 has, but does not contain the indazolyl substitution, in 10 ml of a 1: 3 solvent mixture of tricresyl phosphate and ethyl acetate was dissolved. The obtained solution was treated in the same manner as in the case of Example 4, Sample A.

For verification, a sample B was produced in the same way, however, instead of the coupler no * 3 according to the invention in Coupler mixture 1.65 g of one identical in structure to it the coupler was used, but not the indazolyl substitution exhibited.

Samples A and B were exposed in the usual way, with the the same developer developed as in Example 1 and then bleached, fixed and washed with water in the usual manner, with the results given in the attached drawing

were obtained. This drawing is a graphic representation and shows the density of a cyan dye against red Light in each stage described therein, where the abscissa is the amount of exposure (log E) and the ordinate is the density of the Specify the dye. It can be seen from the drawing that in the case of sample A, the straight-line part of the characteristic curve a little longer and that the gamma is a little lower than that of the Sample B. It should be noted, however, that Sample A at all does not have the adverse effect of desensitization or the like and that it is remarkable is effective as a so-called DIE (development inhibitor-releasing type) coupler. ". <" - ·.

Patent claims:

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Claims (2)

Patent claims (yL Process for the production of cyan images by exposure of a color photographic recording material and development, characterized in that .a light-sensitive, color photographic recording material with at least one silver halide emulsion layer containing a compound of the general formula where A is a cyan image forming coupler radical with a ςί-naphthol or phenol nucleus, the group. . . \ II t Z C - is bonded in the p-position to the hydroxyl group of A and Z is a necessary to form an indazolyl G group Represents atom grouping, ' ■ image-wise "is exposed and color developed, or that a light-sensitive, color photographic recording material imagewise exposed and color developed using a color developer which is a compound of the above general formula I contains. 2. The method according to claim 1, characterized in that the compound of the general "formula I is a compound of the general formula " COIiHH N CH- III ORIGINAL INSPECTED -19- 209848/0996 - - - is where Z has the same meaning as above and R is Alkyl, aryl or a group of the formula stands, where H _{2 is} hydrogen or alkyl and the symbols m and η each stand for whole numbers. 3 · Process according to claims 1 to 2, characterized in that that the compound of general formula I 1-Hydroxy-4- (2 ■ -indazolyl) -N- [<f (2,4-di-tert-amylphenoxy) - -tutyl3-2-naphthamide; · '" i-Hydroxy-4- j2 ^l - (5-chloroindazolyl)) - ir- (n-dodecyl) - j ■■ "" "/ 12-baphthamide; ■ · ' ' \ i-HydiOxy-4- (2 ^t - (6-nitroindazolyl)) - K-i4' (2 _i 4-di-tert- \ amylplienoxy) - "butylj-2-iiaphthamiä \ : '*'"" j 1-% hydroxy-4- (2 ^l - (6-aminoindazolyl) 3-li- ( ₍ r (2,4-di-tert-I amylphenoxy) -butylI-2-naphthamide; j ^f i-iiydroxy-4- (2 '- (e-acetaminoindazolyl)) -! ^^, 4- ^! ai-tert-amylphenoxy) -butr / l J-2-naphtttamide; '■■ i-% droxy-4- (2 ^l - (6-chloroindazolyl)] - 4 ^l - (4-tert ~, ^: , butylpiienoxy)> - 2-naphthaiilid · .;. · i-Hydroxy-4- (2 '- (6-nitroindazolyl)} - l! i- (n-dodecyl) -' 2 ~ naphthamide ·; "" ■ .-. ■. - .- i-Hydroxy-4- (2 '- (5-chloroindazolyl) J-N- (2'-e naphthamides; 2-naphthanilide and / or 1-Η ^^ Γθχν-4- (2
naphtiiamid .is 2 0 9 8 4 8 / Π 9 8 6 ■ ORIGINAL INSPECTED Blank page