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US3385700A
US3385700A US46302965A US3385700A US 3385700 A US3385700 A US 3385700A US 46302965 A US46302965 A US 46302965A US 3385700 A US3385700 A US 3385700A
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cyclohexadienone
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Willems Jozef Frans
Poot Albert Lucien
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Gevaert Photo-Producten NV
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Gevaert Photo-Producten NV
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/72Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Description

United States Patent "ice 3,385,700 RECORDING PROCESS Jozef Frans Willems and Albert Lucien Poot, Wilrijk-Antwerp, Belgium, assiguors to Gevaert Photo-Producteu,

Mortsel, Belgium, a Belgian company i No Drawing. Filed June 10, 1965, Ser. No. 463,029 Claims priority, application Great Britain, June 12, 1964,

24,520/ 64 11 Claims. (Cl. 96-27) The present invention relates to a process for recording optical information by means of a material containing a cyclohexadienone compound.

We have found that a light-sensitive system based on the phototransformation of a cyclohexadienone compound into a compound, which is reactive with a nucleophilic reagent, can be used for recording and reproducing optical information.

It is an object of the present invention to provide a photographic process using a recording medium containing a cyclohexadienone compound.

It is a further object of the present invention to provide a photographic material having a water-permeable layer containing a 3,5-cyclohexadienone compound having in orthoposition to the oxo group at least one acetoxy group or a 2,5-cyclohexadienone compound having in para-position to the 0x0 group at least one acetoxy group preferably a compound according to the following general formulae respectively:

wherein R represents an acetoxy group,

R represents hydrogen, or a hydrocarbon group e.g. alkyl or aryl, an ether group or an acetoxy group,

each of R R R and R represents hydrogen, or a hydrocarbon group e.g. alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert. butyl, or isoamyl, an aryl group or substituted aryl group, acetyl or allyl,

whereby R and R together may represent the atoms necessary to close an aromatic ring,

R and R, as well as R, and R together may represent the atoms necessary to close a homocyclic saturated ring, and

each of R',, R ,R R' and R' represents hydrogen, alkyl or aryl, and

R represents an acetoxy group.

Compounds according to the first general formula, which are particularly suited for use according to the present invention, have the following structural formulae:

3,385,700 Patented May 28, 1968 A compound according to the second general formula, which is particularly suited for use according to the present invention is represented by the following structural formula:

The compounds formed on exposing the above-mentioned cyclohexadienone compounds are ketene intermediates.

According to a first type of recording and reproduction method a visible image can be produced in a photographic element containing one of said cyclohexadienone compounds, by image-wise or record-wise U.V.-irradiating said element thereby transforming said cyclohexadienone compound into a ketene compound, which is reactive with a nucleophilic reagent, and by allowing said ketene compound to react with said nucleophilic reagent to produce a condensation product, which can be detected by means of a colour reaction, thereby forming a coloured product on the exposed areas.

According to a particular photographic reproduction method falling within the scope of this first type, the ketene compound formed by exposure is allowed to react in the photographic element with water, resulting in the image-wise formation of a diene acid. The image-wise formed acid can now be used to produce a visible image e.g. by detecting the acid with suitable pH-indicators, which undergo a colour change under the influence of the hydrogen atoms.

According to a modified method of the said first type of photographic reproduction, the image-wise formed acid can be used to neutralise abase image-wise, whereby the non-neutralised base on the unexposed areas can e.g. be detected by means of a pH-indicator.

According to another modified method of the said first type of photographic reproduction it is possible to produce an image-wise bleach-out reaction by using in the photographic element the said cyclohexadienone compound together with a base and a coloured pH-indicator, which at a lower pH-value is transformed into a colourless compound.

Classes of pH-indicators, the representatives of which are suited for being applied in the present invention, are e.g. nitrophenols, azo compounds, phthaleins and sulphophthaleins.

Further it should be remarked that the image-wise pH- difierentiation obtained according to one of the types of the foregoing photographic reproduction methods can in principle be used to produce image-Wise a pH-dependent colour reaction or to form substances building up an image by using the catalysing influence of the image-wise produced hydrogen ions or image-wise neutralised hydroxyl ions.

According to a second type of recording and reproduction method, a visible image can be produced in a photographic element containing one of said cyclohexadienone compounds by image-wise or record-wise U.V.-irradiating said element thereby transforming said cyclohexadienone compound into a ketene compound, which on the exposed areas blocks the chemical reactivity of a reactant, which is incorporated in the said element before or after exposure, and after exposure allowing the residual reactant to react at the unexposed areas with a reaction agent to form a coloured product.

According to a particular photographic reproduction method falling within the scope of the second-mentioned type of reproduction method, the ketene compound formed on exposing a cyclohexadienone compound is allowed to react with a colour coupler possessing a reactive function with respect to a-coupler coupling agent which may be incorporated in the same material. The colour coupler is chosen such that the reactive radical thereof is blocked by reaction with the ketene compound formed on exposure and is thus excluded from any reaction with a colour coupling agent on the exposed parts. By treating now the exposed material with a suitable colour coupling agent, image-diiferentiation is obtained.

Suitable colour couplers are colour couplers having a coupling function of the nucleophilic type e.g. colour couplers containing reactive hydrogen atoms in the coupling position, such as the colour-forming compounds containing a reactive methylene or phenolic hydroxyl group capable of reacting with the oxidation products of primary aromatic amino coupling developers. Particularly suitable colour couplers are those of the phenol or naphthol type.

The cyclohexadienone compounds used in the process of the present invention can be prepared according to known techniques. As an illustration thereof references of the preparation are given hereinafter.

Monatsh. Chemie:

The cyclohexadienone compounds used in the present invention are mainly U.V.-sensitive. The rate of phototransformation is relatively the highest in the wavelength range of 300 m,u-432 me.

A photographic material for copying purposes according to one of the above-described recording and reproduction methods can be prepared by coating a cyclohexadienone compound from a solution or dispersion onto -a support, which may be more or less porous, e.g. a paper support or can be prepared by incorporating a cyclohexadienone compound into a liquid-permeable layer, preferably a water-permeable layer in order to allow the diffusion therein of chemical reactants. For preparing waterpermeable layers, preferably binding agents are used, which are only slightly or almost not Water-soluble at room temperature but which form water-permeable layers when coated from a solution in an organic solvent e.g. ethanol. Suitable binding agents are e.g. ester gums, which are freed from resinous and waxy substances, and cellulose derivatives forming water-permeable layers such as ethylcellulose and collodion.

Preferably the cyclohexadienone compound is incorporated in non-migratory form into a liquid-permeable layer or support.

Known colour couplers used in multilayer systems in principle are made non-migratory by joining long chain groups to their molecules. In principle this is also possible for the cyclohexadienone compounds (and colour reactants if any) incorporated in photographic material for carrying out the present invention.

It is therefore possible in principle to produce multicolour images in accordance with the present invention in a multilayer material wherein e.g. in a first layer a yellow image, in a second layer a magenta image and in a third layer a cyan image can be formed by applying in said layers a yellow, magenta and cyan colour coupler respectively and carrying out a reproduction process of the second type referred to above.

The following examples illustrate the present invention.

Example 1 A mixture of the following composition:

8 cm. of a 3% solution in ethanol of ester gum freed from resin and wax 1 cm. of a 9% solution of 2-acetoxy-2-methyl-3,5-cyclohexadiene-l-one in acetone 1 cm. of a 0.4% solution of p-nitrophenol in acetone is applied to a baryta-coated paper support in such a way that 1 g. of cyclohexadienone compound is present per sq. m.

The dried layer is treated with a solution of 0.4 g. of sodium hydroxide and 1 g. of lauryl sulphate as wetting agent in a mixture of 90 cm. of ethanol and 10 cm. of water. After having been dried to the air, the photographic material has a yellow colour.

The photographic material is exposed for 2 min. through a black-and-white diapositive of a line original with the aid of a Philips ultra-violet-radiating bulb of watts placed at a distance of 10 cm.

At the exposed areas the material has turned from yellow to colourless.

Example 2 A mixture of the following composition:

8 cm. of a 3% solution of the ester gum of Example 1 in ethanol 1 cm. of a 9% solution of the cyclohexadienone compound of Example 1 in acetone 1 cm. of a 0.4% solution in ethanol of Alizarin Yellow R having the following structure:

OONa

is applied to a baryta-coated paper support in such a way that 1 g. of cyclohexadienone compound is present per sq. m.

The dried layer having a red colour is exposed as described in Example 1.

At the exposed parts the red colour has turned to yellow.

Example 3 A mixture of the following composition:

8 cm. of a 3% solution of the ester gum of Example 1 in ethanol 1 cm. of a 9% solution of the cyclohexadienone compound of Example 1 in acetone 1 cm. of a 0.4% solution in ethanol of phenolphthalein is coated on a bartya-coated paper support in such a way that 1 g. of cyclohexadienone is present per sq. m.

The dried layer is treated with an alkaline solution as described in Example 1.

During exposure as described in Example 1, the exposed parts turned from red to colourless. In this way a positive image is obtained.

Example 4 A mixture of the following composition:

8 cm. of a 3% solution of the ester gum of Example 1 in ethanol 1 cm. of a 9% solution of the cyclohexadienone compound of Example 1 in acetone 1 cm. of a 0.4% solution of Bromothymol Blue (dibromothymol sulphophtalein, sodium salt) in ethanol is applied to a baryta-coated paper support in such a way that 1 g. of cyclohexadienone is present per sq. m.

The dried layer is exposed as described in Example 1.

At the exposed areas the colour turned from blue to yellow.

Very good results are also obtained by substituting Cresol Red (o-cresol sulphophthalein, sodium salt), Chlorophenol Red, or Bromocresol Purple (dibromoo-cresol sulphophthalein, sodium salt) for Bromothymol Blue.

Example 5 A mixture of the following composition:

8 cm. of a 3% solution of the ester gum of Example 1 in ethanol 1 cm. of a 9% solution of the cyclohexadienone compound of Example 1 in acetone 1 cm. of a 0.4% solution of eosin (sodium salt) in ethanol is applied to a baryta-coated paper support in such a way that 1 g. of cyclohexadienone is present per sq. m.

The dried layer is exposed as described in Example 1 but for 5 min.

At the exposed areas the colour turned from red to pink.

Example 6 A mixture of the following composition:

8 cm. of 3% solution of ester gum (freed from resin and wax) in ethanol 1 cm. of a 9% solution of the cyclohexadienone compound of Example 1 in acetone 1 cm. of a 0.1% aqueous solution of the oxonol compound having the following structure:

is applied to a baryta-coated paper support in such a way that 1 g. of cyclohexadienone compound is present per sq. in.

After having been dried to the air, the layer is exposed as described in Example 1.

The colour of the exposed areas turned from colourless to blue.

Example 7 A mixture of the following composition:

8 cm. of 3% solution of ester gum (freed from resin and wax) in ethanol cm. of a 9% solution of the cyclohexadienone compound of Example 1 in acetone cm. of a 4% aqueous solution of sodium hydroxide containing 0.4% of the oxonol compound having the following structure:

COOH

N N 0=o HO-( l p1 nae-hi3=oH-orr=orrorr=orr-o-o-om is applied to a baryta-coated paper support in such a way that 1 g. of cyclohexadienone compound is present per sq. m.

After having been dried to the air, the layer is exposed as described in Example 1.

At the exposed areas the colour has turned from colourless to blue.

By treating then the material with an 0.1 N aqueous solution of hydrogen chloride, the blue image areas hecome reddish brown.

Example 8 If in the foregoing example the mentioned oxonol compound is replaced by one havin the following structure:

on on 2 cm. of a 0.2% solution in dimethylformamide of a compound having the following structure:

CH: O s neonll (IE-011:0

is applied to a baryta-coated paper support in such a way that 1 g. of a cyclohexadienone compound is present per sq. m.

The material dried to the air is exposed as described in Example 1. A positive purple image is obtained.

Example 10' A mixture of the following composition:

9 cm. of a 3% ethanolic solution of the ester gurn of Example 1 1 cm. of a 9% solution of the cyclohexadienone compound of Example 1 in acetone 2 cm. of a 0.2% solution in dimethylformamide of is applied to a baryta-coated paper support in such a way that 1 g. of a cyclohexadienone compound is present per sq. m.

The material dried to the air is exposed as described in Example 1, but for 1 min. only. A green positive image is formed. A visually detectable image-differentiation is already present after an exposure time of 5 seconds.

7 Example 11 A mixture of the following composition:

8 cm. of a 3% ethanolic solution of the ester gum of Example 1 1 cm. of a 9% solution of a cyclohexadienone compound of Example 1 in acetone 1 cm. of a 0.4% solution in ethanol of 4,4-bis-dimethylamino-3"-chlorotriphenylcarbonol is applied to a baryta-coated paper support in such a way that l g. of cyclohexadienone compound is present per sq.m.

On drying to the air the material obtains a greenish tone.

By exposure to U.V.-light the exposed parts are bleached. The greenish tone, however, re-appears by contact of the material with atmospheric oxygen. By treating the exposed material for 30 sec. in a 0.05 N hydrogen chloride solution and rinsing with water for 2 min., the unexposed image areas are bleached, while on the exposed areas a very stable green colour is obtained. Surprisingly an alkaline treatment gives the same result.

An image of the same quality is obtained with the 4,4'-bis-dimethylaminotriphenylcarbinol.

Example 12 A mixture of the following composition:

7 cm? if a 3% ethanolic solution of the ester gum of Example 1 1 cm. of a 9% solution of the cyclohexadienone compound of Example 1 in acetone 2 cm. of a 1% ethanolic solution of a-naphthol Example 13 A mixture of the following composition:

7 cm. of a 3% ethanolic solution of the ester gum of Example 1 1 cm. of a 9% solution of the cyclohexadienone compound of Example 1 in acetone 2 cm. of a 2% aqueous solution of a colour coupler having the following structure:

CONE-O l SOaNa SOaNa 1 cm. of a 2.5% solution of diethyl-p-phenylenediamine hydrochloride,

is applied to a baryta-coated paper in such a way that 1 g. of cyclohexadienone compound is present per sq. m.

The dried layer is exposed as described in Example 1, except that the exposure time is only 1 min. The exposed material is developed in a solution of potassium hexacyanofer-rate'(III) in water/ethanol .(80/20). A greenish positive image is obtained.

8 Example 14 A mixture of the following composition:

7 cm. of a 3% ethanolic solution of the ester gum of Example 1 1 cm. of a 9% solution of the cyclohexadienone compound of Example 1 in acetone 2 cm. of a 2% aqueous solution of the colour coupler of Example 13 Example 15 A mixture of the following composition:

7 cm. of a 3% ethanolic solution of the ester gum of Example 1 1 cm. of a 30% solution of the cyclohexadienone compound of Example 1 in acetone 2 cm. of a 2% ethanolic solution of the colour coupler having the following structural formula:

S OsNB,

1 cm. of a 2.5% aqueous solution of diethyl-p-phenylene diamine hydrochloride is applied to a baryta-coated paper in such a way that 1 g. of the cyclohexadienone compound is present per sq. m. The dried layer is exposed as described in Example 1, and developed by treatment with a 10% alkaline solution (pH=9) of potassium hexacyanoferrate (III) A positive cyan image is obtained.

Example 16 A mixture of the following composition:

20 cm. of a 4% aqueous solution of poly(vinyl alcohol) 2.5 cm. of a 20% solution of the cyclohexadienone compound of Example 1 in acetone 2.5 cm. of a 8% solution of 8-hydroxy quinoline in ethanol is applied to a baryta-coated paper in such a way that 1 g. of the cyclohexadienone compound is present per sq. m.

The dried layer is exposed as described in Example 1 and developed by dipping in a 5% aqueous iron(III) chloride solution. First a positive image is obtained. By rinsing with water and drying to the air the image is reversed:

Example 17 A mixture of the following composition:

20 cm. of a 4% aqueous solution of poly(vinyl alcohol) 2.5 cm. of a 20% solution of the cyclohexadienone compound of Example 1 in acetone 2.5 cm. of a 8% solution of hydroquinone in ethanol is applied to a baryta-coated paper in such a way that 1 g. of the cyclohexadienone compound is present per sq. m.

The dried layer is exposed as described in Example 1. The exposed material is developed with an ammoniacal silver nitrate solution. Immediately after the contact with said solution, a positive image is formed, which, however, disappears very rapidly in favour of a reversal image.

With gallic acid and pyrogallol similar results are obtained as with hydroquinone.

Example 18 A mixture of the following composition:

3 cm. of a 2% solution of 4,4'-bis-dirnethy1amino-3"- chlorotriphenylcarbinol in acetone.

2 cm? of a 9% solution of 2,2-diacetoxy-4-methyl-3,5-

cyclohexadiene-l one in acetone Example 19 A mixture of the following composition:

7 cm. of a 15% ethanolic solution of the ester gum of Example 1 3 cm. of a 10% solution of 2-acetoxy-2-methyl-3,S-cyclohexadiene-1one in acetone 3 cm. of a 1% solution of a-naphthol in acetone is applied to a baryta-coated paper support.

After having been dried to the air, the layer is exposed as described in Example 1 and treated with an alkaline coupling solution as described in Example 12.

A stable positive brown image is obtained. The background has a pale brown colour.

Example 20 A mixture of the following composition:

7 cm. of a solution of ethylcellulose in acetone 2 cm. of a 10% solution of the cyclohexadienone compound described in Example 18 in acetone 1 cm. of a 2% aqueous solution of a colour coupler as described in Example 13 is applied to baryta-coated paper support.

The dried layer is exposed and developed as described in Example 13.

A greenish positive image is obtained.

Example 21 A mixture of the following composition:

2 cm. of a 10% solution of 4-acetoxy-4-methyl-2,5-

cyclohexadiene-l-one in acetone 3 cm. of a 2% solution of a carbinol base as described in Example 18 in acetone is applied to a baryta-coated paper support.

On drying to the air the material obtains a greenish tone.

The exposure and development is carried out as described in Example 18.

At the exposed areas a very stable green colour is obtained.

Example 22 A mixture of the following composition:

7 cm. of a 5% solution of ethylcellulose in acetone 2 cm. of a 7.5% solution of the cyclohexadienone compound having the following structural formula:

1 cm. of a 2% aqueous solution of the colour coupler as described in Example 13 is applied to a baryta-coated paper support.

The dried layer is exposed and developed as described in Example 13.

A greenish positive image is obtained.

From the foregoing it will be seen that the invention permits positive copies to be obtained directly from positive original documents, or from negative originals, according to the ingredients of the recording material.

While reference has been made to processes in which the image is produced in the recording material, which is image-wise or record-wise exposed to the radiation, this is not essential since the selective transformation of the cyclohexadienone compound to ketene in one material can be made to form a visible image in another material, which may itself embody the nucleophilic agent or such agent and a pH-indicator or colour coupler, e.g. by bringing the two materials together in face to face contact while wet, either during or after the exposure step, and then peeling the materials apart.

The invention is, of course, not only applicable to the making of images of readable matter but can be applied for recording any selective exposure pattern such as optical signals.

We claim:

1. A photographic process comprising the step of image-wise or record-wise exposing to U.V.-radiation an element containing as U.V.-sensitive compound a 3,5- cyclohexadienone compound containing in ortho-position to the oxo group at least one acetoxy group or a 2,5- cyclohexadienone compound containing a para-position to the oxo group at least one acetoxy group.

2. A photographic process according to claim 1, wherein the element also contains a nucleophilic reagent capable of reacting with a compound formed by exposing the said cyclohexadienone compound to U.V.-radiati0n.

3. A photographic process according to claim 1, wherein said element contains a cyclohexadienone compound corresponding to one of the following general formulae:

wherein:

R represents an acetoxy group,

R represents a member selected from the group consisting of hydrogen, a hydrocarbon group, an ether group and an acetoxy group,

each of R R R and R represents a member selected from the group consisting of hydrogen and a hydrocarbon group,

each of R' R R' R' and R' represents a member selected from the group consisting of hydrogen, an alkyl and an aryl group,

R' represents an acetoxy group, and wherein R and R may represent the atoms necessary to close an aromatic ring, and

R and R as well as R, and R together may represent the atoms necessary to close a homocyclic saturated ring.

4. A photographic process according to claim 1, com prising the further step of detecting by colour reaction the reaction product formed by reaction between a nucleophilic reagent and the compound formed on exposing to U.V.-radiation said cyclohexadienone compound.

5. A photographic process according to claim 2, wherein the nucleophilic reagent is reagent is reacted in situ with the compound formed by interaction of actinic light on the cyclohexadienone compound, and the unreacted nucleophilic reagent is reacted with another compound to produce a product absorbing visible light.

6. A photographic process according to claim 2, wherein the nucleophilic reagent is water and the detection of the reaction product is carried out by means of a pH-indicator.

7. A photographic process according to claim 2, wherein the nucleophilic reagent is a colour coupler having a reactive hydrogen atom in the coupling position.

8. A photographic process according to claim 2, wherein the nucleophilic reagent is a colour coupler having a reactive methylene or phenolic hydroxyl group capable of reacting with the oxidation products of a primary aromatic amino coupling developer.

9. A photographic process according to claim 2, wherein the nucleophilic reagent is a carbinol base.

10. A photographic process according to claim 2, wherein the nucleophilic reagent is a phenolic hydroxyl groupcontaining photographic developer and the exposed material is developed by means of an ammoniacal silver nitrate solution.

11. A recording material comprising a layer, that incorporates a 3,5-cyclohexadienone compound containing in ortho-position to the oxo group at least one acetoxy group or a 2,5-cyclohexadienone compound containing in para-position to the OX0 group at least one acetoxy group and that also incorporates a nucleophilic agent in the form of a colour coupler with groups that can react directly or indirectly with a ketene formed by exposure of the cyclohexadienone compound to ultra-violet radiation and thereby cease to be available for reaction with a colour coupling agent.

No references cited.

NORMAN G. TORCHIN, Primary Examiner.

J. E. EVERETT, Assistant Examiner.

Claims (2)

1. A PHOTOGRAPHIC PROCESS COMPRISING THE STEP OF IMAGE-WISE OR RECORD-WISE EXPOSING TO U.V.-RADIATION AN ELEMENT CONTAINING AS U.V.-SENSITIVE COMPOUND A 3,5CYCLOHEXADIENONE COMPOUND CONTAINING IN ORTHO-POSITION TO THE OXO GROUP AT LEAST ONE ACETOXY GROUP OR A 2,5CYCLOHEXADIENONE COMPOUND CONTAINING A PARA-POSITION TO THE OXO-GROUP AT LEAST ONE ACETOXY GROUP.
2. A PHOTOGRAPHIC PROCESS ACCORDING TO CLAIM 1, WHEREIN THE ELEMENT ALSO CONTAINS A NUCLEOPHILLIC REAGENT CAPABLE OF REACTING WIITH A COMPOUND FORMED BY EXPOSING THE SAID CYCLOHEXADIENONE COMPOUND TO U.V.-RADIATION.
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US4101323A (en) * 1975-03-27 1978-07-18 Hoechst Aktiengesellschaft Radiation-sensitive copying composition
US4902603A (en) * 1987-10-05 1990-02-20 Olin Corporation Photoresist compositions containing selected 6-acetoxy cyclohexadienone photosensitizers and novolak resins
US5616443A (en) * 1993-08-05 1997-04-01 Kimberly-Clark Corporation Substrate having a mutable colored composition thereon
US5643356A (en) * 1993-08-05 1997-07-01 Kimberly-Clark Corporation Ink for ink jet printers
US5645964A (en) * 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US5681380A (en) 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
US5685754A (en) * 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and polymer coating applications therefor
US5700850A (en) * 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US5721287A (en) 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5733693A (en) 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5739175A (en) * 1995-06-05 1998-04-14 Kimberly-Clark Worldwide, Inc. Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5747550A (en) * 1995-06-05 1998-05-05 Kimberly-Clark Worldwide, Inc. Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5773182A (en) 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US5782963A (en) 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5786132A (en) 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
US5798015A (en) * 1995-06-05 1998-08-25 Kimberly-Clark Worldwide, Inc. Method of laminating a structure with adhesive containing a photoreactor composition
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US5885337A (en) 1995-11-28 1999-03-23 Nohr; Ronald Sinclair Colorant stabilizers
US6168655B1 (en) 1995-11-28 2001-01-02 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6168654B1 (en) 1996-03-29 2001-01-02 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
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US6099628A (en) 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6277897B1 (en) 1998-06-03 2001-08-21 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6503559B1 (en) 1998-06-03 2003-01-07 Kimberly-Clark Worldwide, Inc. Neonanoplasts and microemulsion technology for inks and ink jet printing
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6294698B1 (en) * 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
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Also Published As

Publication number Publication date Type
GB1080380A (en) 1967-08-23 application
NL6507549A (en) 1965-08-25 application
US3385703A (en) 1968-05-28 grant
DE1285877B (en) 1968-12-19 application
BE665367A (en) 1965-12-14 grant
FR1477432A (en) 1967-04-21 grant
GB1070863A (en) 1967-06-07 application

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