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Publication numberUS3547646 A
Publication typeGrant
Publication date15 Dec 1970
Filing date18 Dec 1967
Priority date16 Dec 1966
Publication numberUS 3547646 A, US 3547646A, US-A-3547646, US3547646 A, US3547646A
InventorsHori Haruo, Hoshino Shoichiro, Kato Akira, Taguchi Masahiko, Yumiki Keiichi
Original AssigneeKeuffel & Esser Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Light-sensitive imaging material containing hydrazones
US 3547646 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

S ENS.

SENS,

15, 1970 HARUO am ET'AL 3547,64

LIGHT-SENSITIVE IMAGING MATERIAL CONTAINING HYDRAZONES Filed Dec. 18, 1967 I I I i l 300 400 500 600 X- m u. F IG, 2

km IG. 3

(/5 Z LU (I) INVENTORS! HARUO HORI,MASAHH O TAGUCHI, SHOICHIR'O HOSHINO, AKIRA KATO,

BY KEIICHI YUMIKI ATTORNEY United States Patent O M 3,547,646 LIGHT-SENSITIVE IMAGING MATERIAL CONTAINING HYDRAZONES Haruo Hori and Masahiko Taguchi, Hino, Shoichiro Hoshino, Tokyo, and Akira Kato and Keiichi Yumiki,

Hachioji, Japan, assignors to Keuffel & Esser Company,

Hoboken, N.J., a corporation of New Jersey Filed Dec. 18, 1967, Ser. No. 691,333 Claims priority, applifatioggipan, Dec. 16, 1966,

Int. Cl. G630 1/00 US. Cl. 96-90 1 Claim ABSTRACT OF THE DISCLOSURE BACKGROUND OF THE. INVENTION It is known that in a conventional process for sensitizing imaging material comprising color modifiers and lightsensitive photoactivators yielding free radicals on light exposure there is used, for the purpose of increasing the spectral sensitivity of the material, a light sensitive coloring matter such as a dye of the acridine, cyanine, merocyanine or styryl type. Imaging materials of this general type have been widely described, for example in US. Pats. 3,042,515 to 3,042,519; 3,102,027; 3,102,207; and 3,102,810. Such a sensitizing process, however, is employed in order to broaden the effective wave length band response of a printing material and aims at the sensitization for a visible zone. Accordingly, the process may be effectively applied to the case where there is used a tungsten lamp which emits a large amount of visible light, but cannot display successful sensitizing effects in the case of a commercially available diazo copying machine in which ultraviolet light is utilized.

Further, according to the above sensitizing process, since a visible zone is sensitized, the room lamps employed at the time of production and printing operation of imaging materials are restricted in wave length, with the result that the convenience of use is undesirably lowered. In addition, there are brought about such drawbacks that the background of a printing material is greatly stained due to coloration of the light-sensitive coloring matter itself, which is used as a sensitizer, whereby the practical value and photographic quality of the material are lowered.

SUMMARY OF THE INVENTION The present invention is entirely different in object, structure and effect from such sensitizing process as mentioned above. That is, the present method uses a hydrazone compound, represented by the general formula shown later, in a free-radical type imaging material to increase the sensitivity of a light sensitive system within the light-sensitive wave length area inherent to the photo- 3,547,646 Patented Dec. 15, 1970 activator employed (ordinarily 350-420 mg). Thus, in accordance with the present invention, only the sensitivity in the light-sensitive wave length area inherent to a light-sensitive system is increased, and therefore particularly prominent effects can be attained in the case where there are used commercially available diazo copying machines and the like ultraviolet printing machines.

When the present method is employed, printing materials, which have not been able to be printed except from an expensive mercury lamp light source, can be printed at a practical speed by use of a fluorescent lamp light source, and the costs of printing light source and the like can be reduced. A mercury lamp does not become stable unless several minutes have elapsed after lighting and cannot be used immediately .after lighting, whereas a fluorescent lamp becomes stable simultaneously with lighting and can be advantageously used immediately after lighting. According to the present method, therefore, not only the costs of printing light source can be reduced but also the printing operations can be carried out efiiciently.

Further, the light-sensitive wave length area of the printing material of the present invention is in the ultaviolet zone, as mentioned above, and the room lamps employed at the time of production and printing of the printing material may be covered with filters which can shield only ultraviolet light, whereby the operations can be safely effected in considerably bright rooms.

The hydrazone compounds employed in the present method are colorless or slight yellow, and there is little danger that the backgrounds of printing materials are colored and stained or the qualities thereof are degraded.

The hydrazone compounds to be used in the present invention are those which are represented by the general formula R2 R1CONHN=C wherein R is a hydrogen atom, alkyl group, aralkyl group, aryl group or hetero ring; R is an aralkyl group, aryl group or hetero ring; and R is a hydrogen atom,

alkyl group or aryl group. Examples of these compounds are as follows.

(I) Benzaldehyde-benzoylhydrazone:

(II) 4-dimethylaminobenzaldehyde-benzoylhydrazone:

(III) 4,4-bisdimethylaminobenzophenone benzoylhydrazone:

(IV) Benzophenone-benzoylhydrazone:

(V) 4-methoxybenzaldehyde-benzoylhydrazone:

(IX) 4'-dimethylaminobenzaldehyde-l-hydroxy-Z- naphthoylhydrazone:

(X) ,8-Acenaphthane-4-dimethy1amino-benzoylhydra- (XI) 2-furfuralisonicotinoylhydrazone:

(XH) 4-dimethylarninobenzaldehyde-p-methoxybenzoylhydrazone:

(XIII) 4'-dimethylaminobenzoldehyde-stearoylhydrazone:

(XIV) Benzaldehyde-butyroylhydrazone:

(XV) (a-Camphor) -benzoylhydrazone The photoactivators to be used in the light-sensitive printing materials of the present invention, ie. photoactivators capable of yielding free radicals by action of light, may be any of those which have been known heretofore. Typical examples of such photoactivators are as follows:

(A) Compounds represented by the general formula wherein R is a halogen atom, halogen atom or aryl group; and X is a halogen atom. These include, for example:

Carbon tetrachloride Carbon tetrabromide p-Nitrobenzotribromide Bromotrichloromethane Hexabromoethane Benzotrichloride Iodoform 1,1,1-tribromo-Z-methyl-Z-propanol 1,1,2,2-tetrabromoethane 2,2,2-tribromoethanol 1,1,1-trichloro-2-methyl-2-propanol.

(B) Compounds represented by the general formula wherein Rx represents 1-5 substituents on the benzene ring which substituents are selected from the group consisting of nitro, halogen, alkyl, haloalkyl, acetyl, haloacetyl, alkaryl and alkoxy groups, and not all of these substituents are required to be same. These include, for example:

o-Nitro-a,a,a-tribromoacetophenone m-Nitro-ot,a,u-tribromoacetophenone p-Nitro-a,a,a-tribromoacetophenone u,a,a-Tribromoacetophenone a,a,u-m-Tetrabromoacetophenone a,wa-Tribromo-3,4-dichloroacetophenone a,a,ot-p-Tetrabromoacetophenone a, e,a',a',a-Hexabromo-p-diacetylbenzene.

(C) Compounds represented by the general formula R-SO X wherein R is an alkyl or aryl group which may have a substituent; and X is a halogen atom. These include, for example:

1,3-benzene disulfonyl chloride 2,4-dinitrobenzenesulfonyl chloride o-Nitrobenzenesulfonyl chloride n-Nitrobenzenesulfonyl chloride 3,3'-diphenylsulfone disulfonyl chloride Ethanesulfonyl chloride p-Bromobenzenesulfonyl chloride p-Nitrobenzenesulfonyl chloride p-Iodobenzenesulfonyl chloride p-Acetamidobenzenesulfonyl chloride p-Chlorobenzenesulfonyl chloride p-Toluenesulfonyl chloride Methanesulfonyl chloride Benzenesulfonyl chloride m-Nitrobenzenesulfonyl fluoride Benzenesulfonyl bromide.

(D) Compounds represented by the general formula R-SX wherein R is an alkyl or aryl group which may have a substituent; and X is a halogen atom. These include, for example:

2,4-dinitrobenzenesulfenyl chloride o-Nitrobenzenesulfenyl chloride.

(E) Compounds represented by the general formula R1 AC-/-R2 3 wherein A is a heterocyclic compound residue which may have a substituent; and R R and R are selected from the group consisting of hydrogen, chlorine and bromine atoms, and not all of them are hydrogen atoms at a same time. These include, for example:

w,w,w-Tribromoquinaldine w,w-Dibromoquinaldine 2- e,w-tribromomethyl-4-methylquinoline w,w-Dichloromethyl-qinoline w-Bromolepidine 2-w-bromomethyl-isoquinoline a-w,w,w-Tribromomethyl-4-chloropyridine 1-methyl-2-chloromethyl-benzimidazole 2,S-ditrobromomethyl-3,4-dibromothiophene.

(F) Compounds represented by the general formula wherein R is a substituted or unsubstituted aryl or heterocyclic residue; and X X and X are selected from the group consisting of hydrogen, chlorine and bromine atoms, and not all of them are hydrogen atoms at a same time. These include, for example:

Hexabromodimethyl sulfoxide Pentabromodimethyl sulfoxide Hexabromodimethyl sulfone Trichloromethylphenyl sulfone Tribromomethylphenyl sulfone Trichloromethyl-p-chlorophenyl sulfone Tribromomethyl-p-nitrophenyl sulfone 2-trichloromethy1benzothiazolyl sulfone-(Z) 4,6-dimethylpyrimidyl-2-tribrornomethyl sulfone Tetra-bromodimethyl sulfone 2,4-dichlorophenyl-trichloromethyl sulfone 2-methyl-4-chlorophenyl-trichloromethyl sulfone 2,5 -dimethyl-4-chlorophenyl-trichloromethyl sulfone 2,4-dichlorophenyl-tribromomethyl sulfone.

As the color modifiers, there are those usable as the socalled negative-position type which originally are colorless substances but are convertible into a colored state by action of free radicals formed from the above-mentioned photoactivators, and those usable as the so-called positive-positive type which originally are colored substances but are changed in color or are decolored to colorless by action of the free radicals. As these color modifiers, various coloring matters are effectively used, including, for example, amine compounds such as diphenylamine, benzylamine, triphenylamine, N-hydroXyethyl-N-ethylaniline and p,p-methylenebis (N,N-diethylaniline); leuco bases of dyes such as leuco-malachite green, Michlers hydrol and Lcucomethylene Blue; and various dyes of the diphenylmethane, triphenylmethane, thiazine, oxazine, xanthene, anthraquinone, iminonphthoquinone and ammethine types.

The method of the present invention is etfectively applied not only to printing materials in which have been used other known sensitizers, but also to printing materials incirporated with color tone improvers, extenders and binder resins which have heretofore been used in this kind of printing materials.

DESCRIPTION OF DRAWINGS The drawings show typical spectral sensitivity curves for common free radical imaging materials and free radical materials sensitized according to the present invention.

FIG. 1 relates to unsensitized material.

FIG. 2 relates to material sensitized according to prior art.

FIGS. 3 and 4 relate to material sensitized according to the present invention.

6 PREFERRED EMBODIMENTS The present invention concerns means for sensitizing a light-sensitive printing material, characterized by adding to the light-sensitive system a hydrazone compound represented by the aforesaid general formula. The effective amount of said hydrazone compound to be added is at least 0.001 part by weight per part of the photoactivator, and favorable results can be obtained when tre hydrazone compound is added in substantially the same amount as that of the photoactivator.

In the present invention, fixing and the like treatments may be effected in the same manner as in the case of the conventional printing materials.

In short, the characteristics of the present invention reside in that the hydrazone compound added to a lightsensitive system makes it possible to shorten the time of printing with ultraviolet light and to effect printing by use of a weak light source without coloring the background of the printing material.

The following examples illustrate preferred embodiments of the present invention:

EXAMPLE 1 Light-sensitive compositions shown below were individually applied onto a photographic baryta paper and were dried.

(a) Composition for a known unsensitized light-sensitive material:

Tribromomethylphenyl sulfone-10 g. Diethanolaniline30 g. Acetone500 cc.

Methanol500 cc.

(b) Composition of light-sensitive material sensitized with a known sensitizing compound:

Tribromomethylphenyl sulfone-IO g. Diethanolaniline30 g.

Acridine orange5 g.

Acetone500 cc.

Methanol500 cc.

(c) Composition of light-sensitive material employed in the present invention:

Tribromomethylphenyl sulfone-l0 g.

Diethanolaniline-30 g.

4 dimethylaminobenzaldehyde-benzoylhydrazone (sensitizer II)5 g.

Actone--5OO cc.

Methanol500 cc.

(d) Composition of light-sensitive material using known sensitizing coloring matter in combination with a sensitizer of the present invention:

Tribromomethylphenyl sulfone10 g.

Ethanolaniline-30 g.

4 dimethylaminobenzaldehyde-benzoylhydrazone (sensitizer II)-5 g.

Acridine orange5 g.

Acetone-500 cc.

Methanol-500 cc.

The thus obtained light-sensitive printing materials were individually attached with a photographic negative and were exposed for 3 seconds to an 800 w. high pressure mercury lamp at a distance of 5 cm., whereby the materials (c) and (d) gave deep blue positive images whereas the materials (a) and (b) gave mere light blue positive images.

The light-sensitive printing materials bearing individual images obtained in the above were dipped for one minute in a fixing solution of the composition shown below, whereby copies entirely stable to light were obtained. However, the backgrounds of the copies using the materials (b) and (d) were colored to orange to injure the photographic qualities of the copies, whereas the background of the copy using the present material (c) was White Without being colored or stained.

Composition of fixing solution:

Parts by wt. Stannous chloride Hydrochloric acid 1 Water 50 The sensitivity spectra of individual light-sensitive printing materials in this example will be illustrated with reference to the drawings.

FIGS. 1 to 4 show, respectively, the sensitivity spectra of printing materials coated with the light-sensitive emulsions of the compositions (a) to (d) which were used in this example.

FIG. 1 is the sensitivity spectrum of the unsensitized light-sensitive printing material.

FIG. 2 is the sensitivity spectrum of the light-sensitive printing material sensitized according to a known sensitizing process. As is clear from the spectrum, the material was made light-sensitive over a broader wave length band. In contrast to this, the printing material in accordance with the present invention was increased only in the sensitivity of inherent light-sensitive wave length area, as seen in the spectrum of FIG. 3. However, the printing material using, in combination, a sensitizer according to the present invention and that employed in the known process was not only increased in the sensitivity of inherent light-sensitive Wave length area but was also broadened in the light-sensitive wave length band. Thus, it is not objectionable at all to use the sensitizers of the present invention in combination with known sensitizers.

EXAMPLE 2 Under a red safety lamp, a light-sensitive composition shown below was applied onto a photographic baryta paper and was dried.

Hexabromodimethyl sulfone g. Diphenylamine-30 g. Benzophenone-benzoylhydrazone(sensitizer IV)--5 g. Acetone-500 cc.

Methanol-500 cc.

The thus obtained light-sensitive printing material was attached to a photographic negative and was exposed for 3 seconds to an 800 w. high pressure mercury lamp at a distance of 5 cm., whereby a deep blue positive image With a white background was immediately obtained.

The printing material bearing said image was dipped for one minute in a fixing solution of the following compositions to obtain a copy entirely stable to light.

Parts by wt. Stannous chloride 5 Hydrochloric acid 1 Water 50 On the other hand, a control material, prepared according to the above formulation from which the sensitizer compound IV, had been excluded, required seconds in obtaining a positive image of the same intensity by exposure under the same conditions as above.

EXAMPLE 3 In the same manner as in Example 2, a light-sensitive composition shown below was applied onto a photographic baryta paper.

Tribromomethylphenyl sulfone--l0 g.

Diethanolanilineg.

4-dimethylaminobenzaldehyde-benzoylhydrazone (sensitizer II)2 g.

Acetone500 cc.

Methanol500 cc.

The thus obtained light-sensitive printing material was exposed to a 500 w. xenon lamp so that the exposed surface came to have an illuminance of 10,000 luxes and was then subjected to fixing in the same manner as in Example 2, whereby the exposure time could be shortened to of the time required in the case of a conventional printing material.

EXAMPLE 4 In the same manner as in Example 2, a light-sensitive composition shown below was applied onto a photographic baryta paper.

Tribromomethylphenyl sulfone10 g.

Diethanolaniline-30 g.

,B-Acenaphthane-4-dimethylaminobenzoylhydrazone (sensitizer X)-5 g.

Thiourea0.5 g.

Acetone500 cc.

Methanol-50O cc.

When thiourea was added as a color tone modifier, the color tone of the resulting image changed from blue to dark blue upon exposure as in Example 2.

EXAMPLE 5 In the same manner as in Example 2, a light-sensitive emulsion of the composition shown below was applied onto a photographic baryta paper.

Carbon tetrabromidel0 g.

Indole20 g.

4-methoxybenzaldehyde-benxoylhydrazone (sensitizer V)2 g.

Acetone500 cc.

Methanol500 cc.

EXAMPLE 6 In the same manner as in Example 2, a light-sensitive emulsion of the composition shown below was applied onto a photographic baryta paper.

w,w,w-Tribromoquinaldine-10 g.

Leuco malachite green20 g. Benzophenone-benzoylhydrazone (sensitizer IV)-2 g. Acetone-500 g.

Methanol500 cc.

The thus obtained light-sensitive printing material was exposed for 5 seconds to a 500 w. xenon lamp so that the exposed surface came to have an illuminance of 20,000 luxes to obtain a green positive image with a white background. On the other hand, a control material containing no sensitizer required 10 seconds in obtaining a positive image of the same intensity by exposure under the same conditions as above.

EXAMPLE 7 In the same manner as in Example 2, a light-sensitive emulsion of the composition shown below was applied onto a photographic baryta paper.

Hexa'bromodimethyl sulfone0.l g.

Ethyl violet-0.01 g.

fi-Acenaphthane-4-dimethylamino-benzoylhydrazone (sensitizer X) 0.02 g.

Ethanol-5 .0 cc.

The thus obtained light-sensitive printing material was exposed for 10 seconds to a 500 w. xenon lamp so that the exposed surface came to have an illuminance of 20,000 luxes to obtain a bleached colorless (white) negative image with a greenish blue background. On the other hand, a control material containing no sensitizer required 20 seconds in obtaining a negative image of the same extent by exposure under the same conditions as above.

The above examples have been presented for the purpose of illustration and should not be taken to limit the scope of the present invention. It will be apparent that the described examples are capable of many variations and modifications which are likewise to be included within the scope of the present invention as set forth in the appended claim.

What is claimed is:

1. Light-sensitive imaging material comprising:

(a) a light-sensitive halogen-containing organic photoactivator capable of providing free radicals upon exposure to actinic light;

(b) a color modified capable of providing a visible color change, by action of said free radicals;

(c) between about 0.001 and 1.0 part per part of said photoactivator of a sensitizer of the general formula R2 R1CONHN=C/ a wherein R is hydrogen, or an alkyl, aralkyl, aryl or heterocyclic group;

R is an aryl, or heterocyclic group; and

R is hydrogen, or an alkyl or aryl group.

References Cited UNITED STATES PATENTS OTHER REFERENCES Brandenberger: Veroffentl, Chemical Abstracts, col. 4900(21), 1966, vol. 65.

WILLIAM D. MARTIN, Primary Examiner 20 M. R. P. PERFRONE, JR., Assistant Examiner U.S. Cl. X.R.

@ 123 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION patent n 3 547 646 Dated 15 December 1970 Inventoflfl) Haruo Hori. Masahiko Taquchi, Shoichiro Hoshino, Akira Kat and Keiichi Yumiki It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, Line 37 Delete "3,102,207."

Signed and sealed this 13th day of July 1971.

(SEAL) Attest:

figgfiggi-MfigfiTCfiERfl'R. WILLIAM E. SGHUYLER,JR. ng ricer Commissioner of Patents

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3630656 *20 Oct 196928 Dec 1971Bayer AgProcess for the dyeing and printing of metal-containing polyolefin textile materials
US3886211 *5 Mar 197027 May 1975Ciba Geigy CorpCarboxylic acid hydrazide derivatives
US4150987 *17 Oct 197724 Apr 1979International Business Machines CorporationElectrography
US4233209 *15 Nov 197811 Nov 1980Ciba-Geigy CorporationHindered phenol hydrazones and compositions stabilized therewith
US4244604 *23 May 197913 Jan 1981Minnesota Mining And Manufacturing CompanyAliphatic tertiary amine, dithiooxamide, aromatic substituted hydrazones
US4262937 *23 May 197921 Apr 1981Minnesota Mining And Manufacturing CompanyCarbonless imaging system
US4334015 *23 May 19798 Jun 1982Minnesota Mining And Manufacturing CompanyAromatic substituted hydrazones for forming colored complexes with transition metal salts
US5616443 *1 Jun 19951 Apr 1997Kimberly-Clark CorporationToner for electrography
US5643356 *5 Jun 19951 Jul 1997Kimberly-Clark CorporationUnsaturated ketone sensitizer bonded to radiation transorber with color, molecular includent and vehicles
US5643701 *1 Jun 19951 Jul 1997Kimberly-Clark CorporationElectrophotgraphic process utilizing mutable colored composition
US5645964 *5 Jun 19958 Jul 1997Kimberly-Clark CorporationStabilizers
US5683843 *22 Feb 19954 Nov 1997Kimberly-Clark CorporationSolid colored composition mutable by ultraviolet radiation
US5685754 *19 May 199511 Nov 1997Kimberly-Clark CorporationMethod of generating a reactive species and polymer coating applications therefor
US5686503 *22 Jan 199611 Nov 1997Kimberly-Clark CorporationPhotoinitiators
US5739175 *5 Jun 199514 Apr 1998Kimberly-Clark Worldwide, Inc.Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5747550 *5 Jun 19955 May 1998Kimberly-Clark Worldwide, Inc.Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5798015 *5 Jun 199525 Aug 1998Kimberly-Clark Worldwide, Inc.Exposing a photoreactor composition to radiation in which the photoreactor composition comprises a wavelength-specific sensitizer associated with a reactive-species generating photoinitiator
US5811199 *5 Jun 199522 Sep 1998Kimberly-Clark Worldwide, Inc.Exposing photoreactor to radiation; photoreactor comprises wavelength specific sensitizer
US5849411 *5 Jun 199515 Dec 1998Kimberly-Clark Worldwide, Inc.Polymer film, nonwoven web and fibers containing a photoreactor composition
US629469816 Apr 199925 Sep 2001Kimberly-Clark Worldwide, Inc.Photoinitiators and applications therefor
US648622719 Jun 200126 Nov 2002Kimberly-Clark Worldwide, Inc.Zinc-complex photoinitiators and applications therefor
Classifications
U.S. Classification430/339, 564/149, 430/340, 564/151, 564/150, 554/54
International ClassificationG03C1/675
Cooperative ClassificationG03C1/675
European ClassificationG03C1/675
Legal Events
DateCodeEventDescription
25 Mar 1982ASAssignment
Owner name: BANK OF CALIFORNIA N.A. THE; A NATIONAL BANKING AS
Owner name: CHASE MANHATTAN BANK, N.A. THE; A NATIONAL BANKING
Owner name: CHEMICAL BANK, A BANKING INSTITUTION OF NY.
Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808
Effective date: 19820323
Owner name: CONTINENTAL ILLINOIS NATIONAL BANK & TRUST CO., OF
Owner name: SECURITY NATIONAL BANK, A NATIONAL BANKING ASSOCIA
Owner name: CHEMICAL BANK, A BANKING INSTITUTION OF, NEW YORK