Silver halide photographic material

This invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material which is well adapted for rapid processing, and which provides an image of high quality and has high sensitivity.

Conventional methods for exposure of photographic materials to light include an image forming method using a scanner system. Therein, the original is scanned, and a silver halide photographic material is exposed to light based on the resulting image signals to form a negative image or a positive image corresponding to that of the original. Many recording devices which practically use such a scanner system type image forming method are conventionally known. Light sources which are conventionally used for the recording of the scanner system type recording devices include glow lamps, xenon lamps, mercury vapor lamps, tungsten lamps and light-emitting diodes. However, these light sources are disadvantageous in that their output is low and their working life is short. Scanners and laser printers are known where exposure to light is conducted under high illumination conditions using coherent laser beams such as He-Ne laser beams, argon laser beams and He-Cd laser beams as light sources for the scanner system to remedy the above-described disadvantages. However, although providing a high output, these scanners and laser printers are disadvantageous in that the devices are large-sized and expensive and a modulator is required. Additionally, because the illumination source for exposure emits visible light, there is a limit to safelight use for the photographic materials, and handleability is also poor.

On the other hand, semiconductor lasers are small-sized and inexpensive, modulation is easily conducted, and semiconductor lasers have a working life which is longer than that of the foregoing lasers. In addition, a safelight is advantageously used with semiconductor lasers which emit light in the infrared region. Thus, handleability and workability are improved.

Dyes which absorb light in the infrared region are generally used to prevent halation, to thereby reduce blurring of the image due to exposure to infrared light. Practically, the dyes can remain in the photographic material after processing, so long as the dyes do not absorb visible light. However, the dyes usually absorb some visible light, and a residual color is formed when the dyes remain in the photographic material after processing. The formation of the residual color is practically not preferred. Accordingly, water-soluble dyes are used as the antihalation dyes.

When water-soluble dyes are used in layers on the same side of the support as that coated with silver halide emulsions, the dyes diffuse into the silver halide emulsion layers. Consequently, sensitivity is greatly lowered.

To solve this problem, a method has recently been proposed wherein dyes which are decolorizable in the development processing stage are dispersed in the form of fine solid particles to fix the dyes to a specific layer [See, (PCT)WO 88/04794, European Patent (Laid-Open) Nos. 0,274,723A1, 276,566 and 299,435, JP-A-52-92716 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-55-155350, JP-A-55-155351, JP-A-61-205934, JP-A-48-68623, U.S. Pat. Nos. 2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429 and 4,040,841, Japanese Patent Application No. 1-50874, JP-A-2-282244, JP-A-3-167546 and JP-A-4-180057].

However, dyes which absorb light in the visible wavelength region are mainly disclosed in the above patent specifications. Even where dyes which absorb light in the infrared region are disclosed, it has been found that the dyes specifically exemplified therein are not sufficiently fixed to a specific layer.

An object of the present invention is to provide a silver halide photographic material having high sensitivity and providing high image quality, and which photographic material is well adapted for rapid processing.

The above-described object of the present invention has been achieved by providing a silver halide photographic material comprising a transparent support having thereon a dye layer, a hydrophobic polymer layer and at least one light-sensitive silver halide emulsion layer, wherein the dye layer contains at least one dye represented by formulae (I) to (VIII) dispersed in the form of fine solid particles, the dye layer is disposed between the at least one light-sensitive silver halide emulsion layer and the support, the hydrophilic colloid coating weight of the dye layer is 0.5 g/m 2 or less, and the hydrophobic polymer layer is disposed between the dye layer and the support: ##STR1## wherein T 10 , T 11 and T 12 independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a carbamoyl group, an amino group, a sulfonamido group, a carbonamido group, a ureido group, a sulfamido group, a hydroxy group, a vinyl group or an acyl group; R 13 and R 14 independently represent a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, an alkenyl group, an aryloxy group or an aryl group; R 15 and R 16 independently represent a hydrogen atom or a substituent group; and R 17 and R 18 independently represent an alkyl group, an aryl group, a vinyl group, an acyl group, an alkyl group or an arylsulfonyl group; or T 11 and T 12 , R 13 and R 15 , R 14 and R 16 R 17 and R 18 R 15 and R 17 R 16 and R 18 may be combined together to form a ring; ##STR2## wherein R 21 represents a hydrogen atom, an alkyl group, an aryl or a heterocyclic group; R 22 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, COR 24 or SO 2 R 24 ; R 23 represents a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, COOR 24 , OR 24 , NR 25 R 26 , CONR 25 R 26 , NR 25 COR 24 , NR 25 SO 2 R 24 or NR 25 CONR 25 R 26 ; R 24 represents an alkyl group or an aryl group; R 25 and R 26 each represents a hydrogen atom, an alkyl group or an aryl group; L 21 , L 22 and L 23 each represents a methine group; and n 21 represents 1 or 2; ##STR3## wherein X 41 and X 42 each represents a hydrogen atom, a hydroxyl group, a carboxyl group, --COOR 41 , --COR 41 , --CONH 2 , --CONR 41 R42 42 , an alkyl group, an aryl group or a heterocyclic group; Y 41 and Y 42 each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; Z 41 and Z 42 each represents a hydrogen atom, --CN, a carboxyl group, --COOR 43 , --COR 43 , --CONH 2 , --CONR 43 R 44 , --NHCOR 43 , --NHSO 2 R 43 , --SO 2 R 43 , an alkyl group, an aryl group or a heterocyclic group; R 41 and R 43 each represents an alkyl group or an aryl group; R 42 and R 44 each represents a hydrogen atom, an alkyl group or an aryl group; L 41 , L 42 , L 43 , L 44 and L 45 each represents a methine group; and m 41 and n 41 each represents an integer and the sum of m 41 and n 41 is 2; ##STR4## wherein R 51 and R 52 each represents an alkyl group, an alkenyl group or an aryl group; L 51 represents a bonding group formed by bonding five or seven methine groups through conjugated double bonds; Z 51 represents an atomic group required for completing an aromatic ring; and X.sup.⊖ represents an anion; ##STR5## wherein R 61 represents a hydrogen atom, an alkyl group or an aryl group; R 62 , R 63 , R 64 and R 65 each represents a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group or an amino group; L 61 , L 62 , L 63 , L 64 and L 65 each represents a methine group; and m 61 and n 61 each represents an integer and the sum of m 61 and n 61 is 2; ##STR6## wherein L 71 represents nitrogen atom or a group formed by bonding five or seven unsubstituted or substituted methine groups through conjugated double bonds; E represents O, S or N--R 79 ; R 70 and R 79 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydrazino group or a diazenyl group; R 71 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a heterocyclic group; R 72 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an alkynyl group; R 70 and R 79 may be combined together to form a ring; R 73 and R 74 independently represent a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, an alkenyl group, an aryloxy group or an aryl group; R 75 and R 76 independently represent a hydrogen atom or a substituent group; and R 77 and R 78 independently represent an alkyl group, an aryl group, a vinyl group, an acyl group or an alkyl- or arylsulfonyl group; or R 73 and R 75 , R 74 and R 76 , R 77 and R 78 , R 75 and R 77 or R 76 and R 78 may be combined together to form a ring; ##STR7## wherein X 81 represents a hydrogen atom, a hydroxyl group, COOR 87 , CONR 87 R 88 , an alkyl group or an aryl group; Y 82 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or NR 87 R 88 ; Z 81 represents a hydrogen atom, an alkyl group, an aryl group, a cyano group, COOR 89 , CONR 87 R 88 , COR 89 , SO 2 R 89 , NR 88 COR 89 , a nitro group or a pyridyl group; R 81 , R 82 , R 83 and R 84 each represents a hydrogen atom, an alkyl group, OR 89 , NR 89 COR 87 , COOR 89 , CONR 87 R 88 or a halogen atom; R 85 and R 86 each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; and R 87 , R 88 and R 89 each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; or R 81 and R 82 , R 85 and R 86 , R 82 and R 85 , R 83 and R 86 , or R 87 and R88 may be combined together to form a five-membered or six-membered ring; ##STR8## wherein R 91 , R 92 and R 93 each represents a hydrogen atom an alkyl group or an aryl group; Q 1 represents an atomic group required for forming a basic heterocyclic ring; L 91 , L 92 , L 93 , L 94 , L 95 and L 96 each represents a methine group; p 91 , m 91 and n 91 each represents 0 or 1 provided that the sum total of p 91 +m 91 +n 91 is an integer of 2 or more; and the compound of formula (VIII) has at least one member selected from the group consisting of a carboxyl group, a sulfonic acid arylamido group and a phenolic hydroxyl group contained in the molecular structure thereof.

The present invention is illustrated in greater detail below.

In formula (I), examples of a substituent group for R 15 and R 16 include a hydrogen atom, an alkyl group, an alkoxy group and a halogen atom.

In formula (VI), examples of a substituent group for R 75 and R 76 include an hydrogen atom, an alkyl group, an alkoxy group and a halogen atom.

In formulae (I) to (VIII), an alkyl group has preferably 1 to 8 carbon atoms and more preferably 1 to 4 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, hexyl and octyl. Further, the alkyl group may be substituted. Examples of the substituents include an alkyl group, an aryl group, an alkoxy group, a halogen atom, a cyano group, a carboxyl group, a sulfonamido group, a sulfamoyl group, an acyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a hydroxyl group and an alkylsulfonyl group.

In formulae (I) to (VIII), the aryl group is preferably a phenyl group or a naphthyl group and more preferably a phenyl group. The aryl group may be substituted. Examples of the substituents include the substituents for the alkyl group described above.

In formulae (I) to (VIII), the alkoxy group has preferably 1 to 8 carbon atoms and more preferably 1 to 4 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, n-propyloxy and n-butoxy. The alkoxy group may be substituted. Examples of the substituents include an alkyl group, an alkoxy group, an aryl group and a halogen atom.

In formulae (I) to (VIII), the aryloxy group is preferably a phenoxy group or a naphthoxy group and more preferably a phenoxy group. The aryloxy group may be substituted. Examples of substituents include the substituents for the alkyl group described above.

In formulae (I) to (VIII), examples of the heterocyclic group include a pyridyl group, a thienyl group, a furano group and an imidazolyl group.

In formulae (I) to (VIII), examples of the halogen atom include fluorine, chlorine, bromine and iodine. Among these, fluorine, chlorine and bromine are preferred.

In formulae (I) to (VIII), examples of X.sup.⊖ include Cl.sup.⊖, Br.sup.⊖, CF 3 SO 3 .sup.⊖, ClO 4 .sup.⊖, PF 6 .sup.⊖, CH 3 SO 3 .sup.⊖ and CH 3 CO 2 .sup.⊖.

Specific examples of preferred compounds capable of forming a fine solid particle dispersion, represented by formulae (I) to (VII), for use in the present invention include, but are not limited to, the following compounds. ##STR9##

The dyes for use in the present invention can be easily synthesized by the methods described in PCT-WO 88/04794, European Patent (Laid-Open) Nos. 0,274,723A1, 276,566 and 299,435, JP-A-52-92716, JP-A-55-155350, JP-A-55-155351, JP-A-61-205934, JP-A-48-68623, JP-A-3-167546, JP-A-3-7931, JP-A-2-282244, and U.S. Pat. Nos. 2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429 and 4,040,841 and referring to these methods.

The term "dye dispersed in the form of fine solid particles" as used herein refers to a dye contained in a dye layer, which dye has poor solubility in the dye (colored) layer so that the dye can not be present therein in the molecular state, but is present as a solid having a (large) particle size so that the dye substantially does not diffuse within the dye layer.

Methods for preparing the fine solid particle dispersion are described in PCT-W088/04794, European Patent (Laid-Open) (EP) No. 0,276,566A1 and JP-A-63-197943. Generally, the dye is crushed in a ball mill and stabilized by using a surfactant and gelatin.

In the present invention, the dispersion can be prepared according to the method described in JP-A-63-197943.

Namely, 434 ml of water and a 6.7 wt % solution of 53 g of Triton X-200 surfactant ("TX-200" manufactured by Rohm & Haas Co.) are placed into a 1.5 l screw-cap bottle. To the bottle, there are added 20 g of the dye and 800 ml of zirconium oxide (ZrO 2 ) beads (2 mm diameter). The cap of the bottle is tightly closed. The bottle is placed in a mill, and the contents are crushed for 4 days.

The contents are added to 160 g of a 12.5 wt % aqueous solution of gelatin, and placed in a roll mill for 10 minutes to reduce bubbles. The resulting mixture is filtered to remove the ZrO 2 beads. The resulting solid as such is composed of fine particles having an average particle size of about 0.3 μm. Accordingly, the particles are classified by centrifugal separation into particles having a particle size of 1 μm or smaller.

The dye crystallites for use in the present invention have a particle size of preferably 1.0 μm or smaller, more preferably 0.5 μm or smaller and most preferably 0.01 to 0.5 μm.

The dyes are coated in an amount of preferably 5 to 300 mg/m 2 , particularly preferably 10 to 150 mg/m 2 .

The amount of gelatin used in preparation of the dispersion is that amount which provides a coating weight of gelatin (hydrophilic colloid) of 0.5 g/m 2 or less.

The gelatin (hydrophilic colloid) coating weight of the dye layer of the present invention is 0.5 g/m 2 or less, preferably 0.05 to 0.3 g/m 2 .

When the coating weight of the entire hydrophilic colloid of the photographic material is increased, the amount of water absorbed by the photographic material during processing is increased and the load applied to the drying stage is increased. Hence, an increase in the coating weight of the entire hydrophilic colloid is not preferred from the standpoint of rapid processing. Accordingly, the total coating weight of hydrophilic colloid of the photographic material of the present invention is preferably not more than 3 g/m 2 , more preferably 1 to 2.5 g/m 2 per each side of the support. To reduce the total coating weight of the hydrophilic colloid, the dye layer is preferably provided as a subbing layer. The subbing layer contains a hydrophilic colloid to improve adhesion between the support and another hydrophilic colloid layer such as a silver halide emulsion layer. Accordingly, when the dye layer serves as the subbing layer (e.g. the second subbing layer as described below), the dye layer can be provided without increasing the total amount of hydrophilic colloid.

When the coating weight of silver is increased, processing dependence of photographic properties is increased. Accordingly, an increase in the coating weight of silver is not preferred from the standpoint of rapid processing and a reduction in the replenishment rate, both of which have been in demand in recent years. The coating weight of silver is preferably 3 g/m 2 or less, more preferably 2 g/m 2 or less, particularly preferably 0.5 to 3 g/m 2 .

Examples of the transparent support preferably used in the present invention include polyethylene terephthalate film and cellulose triacetate film.

The surface of the support is preferably subjected to a corona-discharging treatment, a glow-discharging treatment or an ultraviolet-irradiation treatment to improve the adhesion between the support and the hydrophilic colloid layer. A first subbing layer comprising, for example, a styrene butadiene latex or a vinylidene chloride latex (hydrophobic polymer layer) is disposed between the dye layer and the support.

Examples of hydrophobic polymers for use in the first subbing layer (hydrophobic polymer layer) include styrene-butadiene copolymers, vinylidene chloride copolymers, water-soluble polyesters and polyacrylic esters. Of these polymers, styrene-butadiene copolymers and vinylidene chloride copolymers are preferred. More preferred are the styrene-butadiene copolymers.

The styrene-butadiene copolymers may be copolymers of styrene and butadiene monomers in a weight ratio of from 9/1 to 1/9, and may optionally comprise a repeating unit derived from a third monomer such as acrylic acid.

The coating weight of the hydrophobic polymer in the first subbing layer is preferably 100 to 1,000 mg/m 2 . The drying temperature of the subbing layer is preferably 80° to 200° C.

An aqueous dispersion (latex) of the hydrophobic polymer for use in the first subbing layer is preferably prepared as a coating solution, and further a crosslinking agent, a surfactant, a swelling agent, a matting agent, an antistatic agent, etc. are optionally added to the aqueous dispersion.

Examples of the crosslinking agent include the triazine compounds described in U.S. Pat. Nos. 3,325,287, 3,288,775 and 3,549,377 and Belgian Patent 6,602,226; the dialdehyde compounds described in U.S. Pat. Nos. 3,291,624 and 3,232,764, French Patent 1,543,694 and U.K. Patent 1,270,578; the epoxy compounds described in U.S. Pat. No. 3,091,537 and JP-B-49-26580 (the term "JP-B" as used herein means an "examined Japanese patent publication"); the vinyl compounds described in U.S. Pat. No. 3,642,486; the aziridine compounds described in U.S. Pat. No. 3,392,024; the ethyleneimine compounds described in U.S. Pat. No. 3,549,379; and methylol compounds. Of these compounds, dichlorotriazine compounds are preferred.

A hydrophilic colloid layer as a second subbing layer is preferably provided on the first subbing layer (hydrophobic polymer layer) in the present invention.

The coating weight of hydrophilic colloid in the second subbing layer is preferably 20 mg/m 2 to 0.4 g/m 2 . The drying temperature of the second hydrophilic colloid layer is preferably 80° C. or more to effect good adhesion of the second layer to the first subbing layer. The drying temperature is 180° C. or lower. When the drying temperature is too high, the amount of the dye from the dye layer taken up by the first subbing layer is increased, and a residual color is formed. More preferably, the drying temperature is not higher than 160° C.

Preferably, a back layer as described in Japanese Patent Application No. 3-145168 is used to balance the drying property with repsect to curling.

That is, a light-insensitive hydrophilic colloid layer containing a hydrophilic colloid as a binder is provided on a second side of the support opposite the side having thereon at least one silver halide emulsion layer, and a hydrophobic polymer layer is provided on the second side of the support further away from the support than the light-insensitive hydrophilic colloid layer, and the light-insensitive hydrophilic colloid layer and the hydrophobic polymer layer are substantially not swollen when contacted with a processing solution (i.e., the thickness of their layers after the drying step is not more than 1.05 times that after completion of the water washing step in the development).

Various additives and methods described in the following patent specifications can be used to prepare the photographic material of the present invention without particular limitation. These additives and methods are described in the cited portions of the patent specifications as follows.

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Item Patent Specification Citations

______________________________________

(1) Silver halide

JP-A-2-68539 (the 6th line from the

emulsion and

bottom of right lower column of page

preparation 8 to the 12th line of right upper

thereof column of page 10); JP-A-3-24537

(the 10th line of right lower column

of page 2 to the first line of right

upper column of page 6, and the 16th

line of left upper column of page 10

to the 19th line of left lower

column of page 11); JP-A-4-107442;

JP-A-2-97937 (the 12th line of right

lower column of page 20 to the 14th

line of left lower column of page

21); JP-A-2-12236 (the 19th line of

right upper column of page 7 to the

12th line of left lower column of

page 8); and JP-A-4-33043.

(2) Chemical JP-A-2-68539 (the 13th line of right

sensitization

upper column of page 10 to the 16th

method line of left upper column of page

10); Japanese Patent Application No.

3-105035; and selenium sensitization

method described in Japanese Patent

Application No. 3-189532.

(3) Anti-fogging

JP-A-2-68539 (the 17th line of left

agent, lower column of page 10 to the 7th

stabilizer line of left upper column of page

11, and the second line of left

lower column of page 3 to left lower

column of page 4);-JP-A-2-103526

(the 19th line of right lower column

of page 17 to the 4th line of right

upper column of page 18, and the

first line to the 5th line of right

lower column of page 18); and thio-

sulfinic acid compounds described

in JP-A-1-237538.

(4) Color tone JP-A-62-276539 (the 7th line of left

improver lower column of page 2 to the 20th

line of left lower column of page

10); and JP-A-3-94249 (the 15th line

of left lower column of page 6 to

the 19th line of right upper column

of page 11).

(5) Spectral JP-B-46-10473 (the 18th line of

sensitizing right column of page 1 to the 24th

dye line of left column of page 2, and

the 23rd line of right column of

page 2 to the 22nd line of left

column of page 6); U.S. Patent

3,482,973 (the 22nd line of the

second column to the 59th line of

the 4th column); U.S. Patent

3,623,881 (the 34th line of the

second column of the 53rd line of

the 7th column); JP-A-59-191032 (the

8th line of right of right upper

column of page 3 to the 9th line of

left lower column of page 3, and the

12th line of right lower column of

page 3 to the bottom of page 7); JP-

A-60-80841 (the 18th line of right

lower column of page 4 to the 6th

line of right lower column of page

12); and JP-A-1-97947 (the first

line of left upper column of page 4

to the 11th line of right upper

column of page 4, and the 11th line

of right lower column of page 4 to

the 6th line of right upper column

of page 8, and the 9th line of left

lower column of page 10 to the

second line of left lower column of

page 11).

(6) Super- JP-A-59-192242 (the 19th line of

sensitizing left lower column of page 10 to the

dye 15th lone of left lower column of

page 12); and JP-A-60-80841 (the

10th line of right upper column of

page 13 to the first line of left

upper column of page 16).

(7) Surfactant, JP-A-2-68539 (the 14th line of left

antistatic upper column of page 11 to the 9th

agent line of left upper column of page

12); JP-A-2-12236 (the 7th line of

right upper column of page 9 to the

7th line of right lower column of

page 9); and JP-A-2-18542 (the 13th

line of left lower column of page 2

to the 18th line of right lower

column of page 4).

(8) Matting agent,

JP-A-2-68539 (the 10th line of left

lubricant upper column of page 12 to the 10th

(i.e., sliding

line of right upper column of page

agent) 12, and the 10th line of left lower

plasticizer column of page 14 to the first line

of right lower column of page 14);

and JP-A-2-103526 (the 15th line of

left upper column of page 19 to the

15th line of right upper column of

page 19).

(9) Hydrophilic JP-A-2-68539 (the 11th line of left

colloid lower column of page 12 to the 16th

line of left lower column of page

12).

(10) Hardening JP-A-2-68539 (the 17th line of left

agent lower column of page 12 of the 6th

line of right upper column of page

13); and JP-A-2-103526 (the 5th line

to the 17th line of right upper

column of page 18).

(11) Dye JP-A-63-49752 (the 4th line of left

lower column of page 18 to the

second line of left upper column of

page 19).

(12) Binder JP-A-2-18542 (the first line to the

20th line of right lower column of

page 3).

(13) Polyhydroxy-

JP-A-3-39948 (left upper column of

benzenes page 11 to left lower column of page

12); EP 452,7-72A; and JP-A-2-55349

(the 9th line of left upper column

of page 11 to the 17th line of right

lower column of page 11).

(14) Polymer latex

JP-A-2-103526 (the 12th line to the

20th line of left lower column of

page 18).

(15) Compound JP-A-2-103526 (the 6th line of right

having an lower column of page 18 to the first

acid group line of left upper column of page

19); and JP-A-2-55349 (the 13th line

of right lower column of page 8 to

the 8th line of left upper column of

page 11).

(16) Hydrazine JP-A-2-12236 (the 19th line of right

nucleating upper column of page 2 to the third

agent line of right upper column of page

7); and compounds of formula (II)

and compounds II-1 to II-54

described in JP-A-3-174143 (the

first line of right lower column of

page 20 to the 20th line of right

upper column of page 27).

(17) Nucleation Compounds of formulas (II-m) to

accelerator (II-p) and compounds II-1 to II-22

described in JP-A-2-103536 (the 13th

line of right upper column of page 9

to the 10th line of left upper

column of page 16); and compounds

described in JP-A-1-179939

(18) Black pepper

Compounds described in U.S. Patent

inhibitor 4,956,257 and JP-A-1-118832

(19) Redox Compounds of formula (I) (particu-

compound larly compounds 1 to 50) described

in JP-A-2-301743; compounds of

formulas (R-1), (R-2) and (R-3) and

compounds 1 to 75 described in JP-A-

3-174143 (pages 3 to 20); and

compounds described in Japanese

Patent Application Nos. 3-69466 and

3-15648.

(20) Monomethine Compounds of formula (II) (particu-

compound larly compounds II-1 to II-26)

described in JP-A-2-287532

(21) Layer JP-A-3-198041

structure

(22) Processing JP-A-2-103037 (the 7th line of right

method upper column of page 16 to the 15th

line of left lower column of page

19); JP-A-2-115837 (the 5th line of

right lower column of page 3 to the

10th line of right upper column of

page 6); and JP-A-2-55349 (the first

line of right lower column of page

13 to the 10th line of left upper

column of page 16

______________________________________

The present invention is now illustrated in greater detail by reference to the following Examples which, however, are not to be construed as limiting the invention in any way.