Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
  • B41M5/506—Intermediate layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

• the present invention refers to a microporous ink-jet recording material comprising a support, at least one non-porous layer coated on the support, and at least one porous ink receiving layer coated on at least one non-porous layer, wherein at least one non-porous layer comprises a color fading inhibitor compound.
• the ink high speed absorptivity can be achieved using an ink-jet recording material comprising a porous layer which is able to rapidly remove the fresh spread ink from the surface of the material, while the absorption capacity can be adjusted varying the thickness of the receiving layer. Even if the ink-jet record materials having porous layers present a better ink absorptivity than ink-jet record materials utilizing swelling system layers, the images printed on porous system may suffer of oxidation deterioration of coloring matter component under natural air exposure.
• the gas circulation in porous materials supplies a continuous flux of oxidizing compounds, such as nitrogen oxides, sulfur oxides, oxygen or ozone gas, that are directly in contact with the coloring matter in the porous layer. Accordingly, images obtained by ink-jet recording materials have inferior properties in terms of storage characteristics, such as light resistance, water resistance and gas resistance, compared to images obtained by silver halide photographic materials.
• oxidizing compounds such as nitrogen oxides, sulfur oxides, oxygen or ozone gas
• images obtained by ink-jet recording materials have inferior properties in terms of storage characteristics, such as light resistance, water resistance and gas resistance, compared to images obtained by silver halide photographic materials.
• the use of conventional antioxidant compounds provide a limited protection in the time that is vanished when the compound is consumed. Most of natural or synthetic antioxidants, like vitamin C, vitamin E, substituted hydroquinone, exhibit positive activity to prevent image discoloration due to oxidation, but have the disadvantage of generating colored substances, as reaction products, that visibly modify the printed image.
• European Patent 875,544 discloses an ink composition comprising a colorant, water, a water-soluble organic solvent, and a fine particle of a polymer, the polymer constituting the fine particle having a film-forming property and, at the same time, an ultraviolet absorbing capacity and/or a light stabilizing capability;
• Japanese Patent application 11-315,234 discloses an ink composition containing a triazine compound and a sterically hindered amine compound;
• Japanese Patent application 05-239,389 discloses a recording liquid comprising a dye, pure water and a light stabilizer capable of obtaining high-grade stabilized images.
• a transferring protective covering material comprising a fluorescent whitening agent, an ultraviolet light absorber, and a light stabilizer to cover a printed image
• US 4,756,963 discloses a transferring protective covering material comprising a flexible substrate, an adhesive layer containing a light stabilizer and a solid resin layer.
• EP 1,186,439 discloses a surface treatment method for recorded matter, such as images recorded on a recording medium and the recording medium that contains such images, which can improve the weather characteristics of the images, such as light resistance and gas resistance. This method is characterized by subjecting the recorded matter to an after-treatment, such as spray treatment, coating treatment, immersion treatment, to form an overcoat layer applied onto the surface of the recorded matter.
• This overcoat layer contains an aqueous solution containing a water- soluble resin, a light resistance improving agent and an ink fixing agent; the overcoat layer protects the surface of the recorded matter preventing the gas present in the air to penetrate into the recorded matter, and thus improving the color fading due to light and gas presence.
• a re-wet liquid solution applied to a dried porous basecoat is disclosed, for example, in US 6,475,612, US 6,432,523 and US 6,423,375, wherein a process that allows the production of multi-layer ink-receiving materials in which one or more topcoats can be applied to a porous basecoat comprising a plurality of pores to produce a uniform and defect-free coating layer is disclosed.
• both the after-treatment solution and the re-wetting solution described above involve the use of a treatment agent; this means that the treatment agent must be incorporated into an additional composition to form the protective layer to be sprayed or coated onto the surface of the recorded matter, before or after that he image is obtained, with the consequent problems related to choose the proper elements contained in the additional composition, how to introduce and mix them, how to store and treat the final composition, and so on.
• the color fading inhibitor compounds directly into the recording elements, without the need to prepare any additional compositions to be sprayed or coated onto the recorded matters.
• Many patents in the art disclose recording elements wherein ink-receiving layers contain chemical compounds to prevent color discoloration.
• EP 1,120,281 discloses an ink-jet recording material comprising pigment particles dispersed in a binder with average particle size of 1 micron or less.
• the ink receiving layer comprises light resistant enhancing agents for image selected from phenolic compounds, boric acid, borate salts and cyclodextrin compounds.
• EP 1,008,457 and US 6,391,428 disclose an ink-jet recording sheet having an image preserving layer comprising anionic colloidal silica and zinc oxide particles; the ink receiving layer also comprises specific sterically hindered amines compounds having alkoxy groups.
• WO 2002-055,618 discloses the use of specific water soluble sterically hindered amine compounds which contain an oxyl or hydroxyl group on the nitrogen atom;
• EP 1 ,031 ,431 discloses a recording medium comprising a specific sterically hindered amine compound having an alkyl group bonded to nitrogen atom of a piperidine ring with interposition of oxygen;
• EP 1,134,087 discloses a recording medium comprising an ink receiving layer containing specific sterically hindered amine compounds exhibiting solubility in water of 0.01 to 5%;
• Japanese Patent applications 61-146,591; 11-245,504 and 2000-247,015 describe recording sheets containing specific sterically hindered amine compounds which show improved light fastness and water resistance.
• ink-jet receiving materials containing color fading inhibitor compounds incorporated in the same layers containing filler such as alumina hydrate or silica compounds, generally exhibit unacceptable coating defects due to interaction between the color fading inhibitor compounds and the filler compounds.
• An other way of solving the problem consists in adding the color fading preventing compound in the base of the ink receiving material.
• US 6,171,751 discloses a laminate base for an imaging element comprising a paper having adhered to each side a biaxially oriented sheet of polyolefin polymer, wherein the top biaxially oriented sheet on the image side has incorporated therein a hindered amine light stabilizer and the top biaxially oriented polyolefin sheet comprises a plurality of layers of polylpropylene.
• EP 1,205,312 discloses a recording medium comprising a base material, and at least one resin selected from a primary amine resin and a secondary amine resin and a sterically hindered amine compound contained in the base material and/or on the surface of the base material, wherein the sterically hindered amine compound does not contain a sterically hindered phenol moiety in its chemical structure.
• EP 1,138,514 discloses a recording material comprising a support coated with a layer containing a light resistance-imparting chemical, and an image-forming layer free of a light resistance-imparting chemical in that order, wherein the light resistance-imparting chemical is selected from inorganic ultraviolet absorbents, organic ultraviolet absorbents or divalent or higher metals, such as zinc oxide, titanium oxide or cerium oxide.
• the light resistance-imparting chemical is selected from inorganic ultraviolet absorbents, organic ultraviolet absorbents or divalent or higher metals, such as zinc oxide, titanium oxide or cerium oxide.
• the present invention refers to a microporous ink-jet recording material comprising a support, at least one non-porous layer coated on the support, and at least one porous ink receiving layer coated on at least one non-porous layer, wherein at least one non-porous layer comprises a color fading inhibitor compound of the following Formula I or its salt:
• Ri to Rio being the same or different, each is an alkyl group having from 1 to 5 carbon atoms;
• X is a divalent linking group;
• m and n, equal or different, are 0, 1 or 2;
• Z is Y or is an alkyl group having from 1 to 12 carbon atoms, and Y is represented by formula II, Formula II
• the color fading inhibitor compounds of Formula I are suitable to improve the weather storage characteristics over time, such as gas resistance, preventing oxidation deterioration of coloring matter component of the printed image during long term exposure to natural air.
• the ink-jet recording material of the present invention allows to obtain colored printed images which are not altered over the time, i.e. a yellowing change is not noted in the printed or not printed images.
• the non-porous layer coated onto the support of the microporous ink-jet recording material of the present invention comprises a binder, a color fading inhibitor compound of formula I or its salt thereof and, preferably, at least one surfactant.
• Suitable binder to be used in the non-porous layer may be, for example, hydrophilic binders, such as polyvinyl alcohol, silanol modified polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, oxidized starch, etherified starch, a cellulose derivative such as carboxymethyl cellulose or hydroxyethyl cellulose, casein, gelatin, acidic gelatin, soybean protein or, maleic anhydride resin, a copolymer latex of conjugated diene type such as a styrene-butadiene copolymer or a methylmethacrylate-butadiene copolymer; an acrylic polymer latex of acrylic type such as a polymer or a copolymer of acrylic ester or methacrylic ester, or a polymer or a copolymer of acrylic acid or methacrylic acid; a polymer latex of vinyl type such as an ethylene-vinyl acetate copo
• binders may be used alone or in combination as a mixture. Further, known natural or synthetic resin binders may be used alone or in combination as a mixture.
• Preferred binders used in the non-porous layer are gelatin, polyvinyl alcohol and polyvinylpyrrolidone.
• the dry content of binder in the non-porous layer is preferably in the range from 10 to 90 by weight %, more preferably from 30 to 70 by weight %.
• the non-porous layer preferably comprises from 0,1 to 10 g/m 2 , more preferably from 0,5 to 8 g/m 2 of binder.
• Ri to R ⁇ 0 each represents a straight or branched alkyl group having from 1 to 5 carbon atoms, such as, for example, methyl group, trifluoromethyl group, ethyl group, propyl group, isopropyl group, butyl group, tert.-butyl group.
• Preferred examples of alkyl groups represented by Ri . to R ⁇ 0 are methyl groups or ethyl groups.
• X when present, is a divalent linking group, such as, for example, straight chain, branched chain or cyclic alkylene, arylene, aralkylene, oxy, oxo, thio, sulfonyl, sulfoxy, amino, imino, sulfonamido, carbonamido, carbonyloxy, urethanylene and ureylene groups and combinations thereof such as sulfonamidoalkylene or carbonamidoalkylene; m and n, equal or different, are 0, 1 or 2.
• Preferred examples of divalent linking groups are alkylene groups.
• Z can be represented by Formula II or by an alkyl group having from 1 to 12 carbon atoms, such as, for example, methyl group, trifluoromethyl group, ethyl group, propyl group, isopropyl group, butyl group, tert.-butyl group, pentyl group, octyl group, nonyl group.
• alkyl groups represented by Z are alkyl groups having froml to 6 carbon atoms.
• R ⁇ and R ⁇ 2 each represents a straight or branched alkyl group having from 1 to 6 carbon atoms, such as, for example, methyl group, trifluoromethyl group, ethyl group, propyl group, isopropyl group, butyl group, tert.-butyl group, pentyl group, hexyl group.
• alkyl groups represented by Ru and R ⁇ 2 are methyl groups, ethyl groups, butyl group or tert.-butyl groups.
• Preferred color fading inhibitor compounds useful in the present invention are represented by the following Formula III: Formula III wherein, Y, Rj and R 6 are as above and Alk is an alkyl group having from 1 to 12 carbon atoms, such as, for example, methyl group, trifluoromethyl group, ethyl group, propyl group, isopropyl group, butyl group, tert.-butyl group, pentyl group, hexyl group.
• Preferred examples of alkyl groups represented by Alk are alkyl groups having from 1 to 6 carbon atoms, such as, for example are methyl groups, ethyl groups, butyl group or tert.- butyl groups.
• the term "group" is used to define a chemical compound or substituent, the described chemical material comprises the basic group, ring or residue and that group, ring or residue with conventional substitutions.
• the term “units” is used, only the chemical unsubstituted material is intended to be included.
• the term “alkyl group” comprises not only those alkyl units such as methyl, ethyl, butyl, octyl, stearyl, etc., but even those units bearing substituents such as halogen atoms, cyano, oxydryl, nitro, amino, carboxilate, solfate or solfonate groups.
• the term “alkyl units” on the contrary comprises only methyl, ethyl, stearyl, cyclohexyl. Examples of color fading inhibitor compounds particularly useful in the present invention are represented by, but not limited to, the following examples.
• the color fading inhibitor compounds useful in the present invention have a solubility in water lower than 0.01%. They are incorporated into the non-porous layer of the ink-jet recording material of the present invention by one of the incorporating methods known in the art, such as, for example, milling or grinding techniques, e.g., ball-milling, sand-milling or colloid-milling the compounds in the presence of a dispersing agent; oil-in-water dispersion method or loaded particle latex techniques, such as those described in Research Disclosure, Item 19551, July, 1980; or by using micro-precipitation techniques to form micro-particulates of the water insoluble color fading inhibitor compound in a water system; or by dissolving them in alcohol solution including, for example, hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, perchloric acid, carbonic acid, a carboxylic acid, such as formic acid and acetic acid, a substituted carboxylic acid, a sulf
• the dry content of the color fading inhibitor compound in the non-porous layer of the ink-jet recording material of the present invention is preferably from 10 to 90 weight %, more preferably from 20 to 70 weight % .
• the amount of the color fading inhibitor compound comprised in the non-porous layer used in the present invention is generally in the range from 0.1 to 10 g/m , preferably from 0.3 to 4 g/m , most preferably from 0.5 to 3 g/m 2 .
• the non-porous layer of the recording material preferably comprises at least a surfactant. Examples of surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and non-ionic surfactants.
• Anionic surfactants comprise an anionic group, such as a carboxyl group, a sulfo group, a phospho group, a sulfuric acid ester group, a phosphoric acid ester group joined to a long chain aliphatic residue.
• anionic surfactants are, for example, alkylcarboxylates, alkylsulfates, alkylsulfhonates, aralkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfuric acid esters, alkylphosphoric acid esters, n-acyl-n-alkyltaurines, sulfosuccinic acid esters, sulfoalkylpolyoxyethylene alkylphenyl ether and polyoxyethylene alkylphosphoric acid esters.
• cationic surfactants include 2-vinylpyridine derivatives and poly-4- vinylpyridine derivatives.
• amphoteric surfactants examples include lauryl dimethyl aminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, propyldimethylaminoacetic acid betaine, polyoctylpoly-aminoethyl glycine, and imidazoline derivatives.
• non-ionic surfactants include non-ionic fluorinated surfactants and non-ionic hydrocarbon surfactants.
• non-ionic hydrocarbon surfactants include ethers, such as polyoxyethylene nonyl phenyl ethers, polyoxyethylene octyl phenyl ethers, polyoxyethylene dodecyl phenyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene oleyl ethers, polyoxyethylene lauryl ethers, polyoxyethylene alkyl ethers, polyoxyalkylene alkyl ethers; esters, such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, and polyoxyethylene stearate; and glycol surfactants.
• ethers such as polyoxyethylene nonyl phenyl ethers, polyoxyethylene octyl phenyl ethers, polyoxyethylene dodecyl phenyl ethers,
• non-ionic surfactants include octylphenoxy polyethoxy ethanols, such as TritonTMX-100, X-l 14, and X-405, available from Union Carbide Co., Danbury, Conn.; acetylenic diols such as 2,4,7,9-tetramethyl-5-decyl-4,7-diol and the like, such as SurfynolTMGA and SurfynolTMCT-136,available from Air Products & Chemicals Co., Allentown, Pa., trimethyl nonylpolyethylene-glycol ethers, such as TergitolTMTMN-10 (containing 10 oxyethylene units, believed to be of formula C 12 H 25 O(C 2 H 4 O) 5 H), available from Union Carbide Co., Danbury, Conn.; non-ionic esters of ethylene oxide, such as MerpolTMSH(believed to be of formula CH 3 (CH 2 )i 2 (OC 2 H 4 ) 8 OH), available from Union
• Merpol 1M LFH (believed to be of formula CH 3 (CH 2 ) n (OC 2 H 4 ) 8 (OC 3 H 6 ) 8 OH, where n is an integer from about 12 to about 16)
• Non-limiting examples of non-ionic fluorinated surfactants include linear perfluorinated polyethoxylated alcohols (e.g., ZonylTMFSN, ZonylTMFSN-100, ZonylTMFSO,and ZonylTMFSO-100available from DuPont Specialty Chemicals, Wilmington, Del.), fluorinated alkyl polyoxyethylene ethanols (e.g., FluoradTMFC-170C available from 3M, St. Paul, MN), fluorinated alkyl alkoxylates (e.g., FluoradTMFC-171 available from 3M, St.
• linear perfluorinated polyethoxylated alcohols e.g., ZonylTMFSN, ZonylTMFSN-100, ZonylTMFSO,and ZonylTMFSO-100available from DuPont Specialty Chemicals, Wilmington, Del.
• fluorinated alkyl polyoxyethylene ethanols e.g.,
• fluorinated alkyl esters e.g., FluoradTMFC-430, FC-431, and FC-740 available from 3M, St. Paul, MN
• fluorine-substituted alkyl esters and perfluoroalkyl carboxylates for example, the F-tergentseries manufactured by Neos Co., Ltd., the Lodyneseries manufactured by Ciba-Geigy, the Monflorseries manufactured by ICI, the Surfluonseries manufactured by Asahi Glass Co., Ltd., and the Unidyneseries manufactured by Daikin Industries, Ltd.).
• Preferred nonionic fluorocarbon surfactants include TritonTMX-100, ZonylTMFSO, FluoradTMFC-170C, and FluoradTMFC-171. These surfactants can be added individually or in combination of two or more thereof.
• the non-porous layer preferably comprises from 0.01 and 1 g/m 2 of the surfactants, and more preferably from 0.02 and 0,8 g/m 2 (da controllare).
• dispersant agents, thickening agents, pH adjuster agents, lubricants, fluidity modifier agents, surface activators, waterproof agents, mold-releasing agents, whitening agents, ultraviolet absorbing agents, antioxidants, hardening agents can be added to the non-porous layer.
• the porous ink receiving layer comprises inorganic pigment fine particles and a binder.
• the inorganic pigment fine particles comprised in the porous ink receiving layer may be inorganic pigment fine particles which are insoluble or hardly soluble in water.
• the inorganic pigment fine particles can be exemplified by inorganic pigments such as calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titania, zinc oxide, zinc carbonate, aluminum silicate, alumina hydrate, magnesium silicate, calcium silicate and silica, any of which may be used alone and also in combination.
• Pigments particularly preferable from the viewpoint of ink absorptivity and image suitability such as image resolution include alumina hydrate, silica and calcium carbonate.
• Alumina hydrate may be represented by the formula Al 2 ⁇ 3 .nH 2 ⁇ ; specifically, the alumina hydrate may be, for example, gibbsite, bayerite, hordostrandite, boehmite, diaspore or pseudoboehmite.
• Alumina hydrate, and in particular boehmite or pseudo-boehmite, (wherein n is from 1.0 to 2.0) is preferably used in the ink-jet recording material used in the present invention.
• the alumina hydrate as described for example in EP patent application No.
• 636,489 can be produced by any conventional method such as the hydrolysis of aluminum alkoxide or sodium aluminate.
• Rocek, et al. [Collect Czech. Chem. Commun., Vol. 56, 1253-1262 (1991)] have reported that the pore structure of aluminum hydroxide is affected by deposition temperature, pH of the solution, aging time and surfactants used.
• the shape of the alumina hydrate can be in the form of a needle or in the form of a flat plate (as described in the literature by Rocek J., et al., Applied Catalysis, Vol.
• the average particle diameter of the alumina hydrate is preferably in the range from 10 to 200 nm, preferably from 50 to 150 nm.
• the dry content of the alumina particles in the micorporous ink receiving layer preferably is from 10 to 95 weight %, more preferably from 15 to 90 weight % ; the ink receiving layer preferably comprises from 10 to 80 g/m 2 , more preferably from 15 to 60 g/m 2 of alumina particles.
• the solvent is preferably water.
• the silica may include natural silica, synthetic silica, amorphous silica, and chemically modified silica compounds, any of which may be used without any particular limitations, but particularly preferable is synthetic fine particulate silica with a specific surface area having preferably from 20 to 700 g/m according to the BET method, and by use of the silica with such specific surface area, excellent color forming characteristic of the water-soluble dye in ink, optimum shape and size of ink dots can be accomplished.
• Silica particles are described, for example, in US 5,612,281 and EP 813,978, which discloses ink-jet recording materials using synthetic silica fine particles prepared by a gas phase process, giving ultrafine particles having an average particle size from several nm to several tens nm, and having characteristics of giving high glossiness and high ink- absorption properties.
• a method for producing a positively charged colloidal silica sol is also disclosed, for example, in EP 1,112,962 and JP-B-47-26959, the method comprising coating the silica surface with alumina. By this method, it is possible to obtain a silica sol having the surface coated with alumina, which is excellent in transparency and stability.
• the content of silica should preferably be at least 10 wt%, more preferably at least 30 wt% in the micorporous ink receiving layer.
• the calcium carbonate may include heavy calcium carbonate, light calcium carbonate and colloidal calcium carbonate, any of which may be used.
• the binder in the porous ink receiving layer may be chosen from the list of the binders cited above to be used in the non-porous layer comprised in the ink-jet recording material of the present invention.
• Preferred binder used in the porous ink receiving layer is polyvinyl alcohol.
• the dry content of binder in the porous ink receiving layer is preferably in the range from 0.5 to 30% by weight, more preferably from 1 to 25% by weight.
• the ink receiving layer preferably comprises from 0,1 to 10 g/m 2 , more preferably from 2 to 8 g/m 2 of binder.
• the content of the binder is preferably from 1 to 50 parts by weight, more preferably from 2 to 25 parts by weight, per 100 parts by weight of the inorganic pigment particles present in the ink jet receiving layer.
• the porous ink receiving layer of the recording material can optionally comprises boric acid or a borate.
• the boric acid not only orthoboric acid but also metaboric acid and hypoboric acid may be used.
• the borate soluble salts of these boric acids are preferably employed.
• the dry amount of boric acid or a borate used in the porous ink receiving layer is generally from 5 to 50 weight %, preferably from 10 to 30 weight %, as calculated as H 3 BO 3 relative to the binder.
• the ink receiving layer preferably comprises from 0.05 to 5 g/m 2 , more preferably from 0.1 to 2 g/m 2 of boric acid or borate.
• the porous ink receiving layer of the recording material preferably comprises at least a surfactant.
• surfactants examples include anionic surfactants, cationic surfactants, amphoteric surfactants, and non-ionic surfactants.
• Useful surfactants to be used in the porous ink receiving layer may be chosen from the list of the surfactants cited above to be used in the non-porous layer comprised in the ink recording material of the present invention.
• Preferred surfactants are nonionic fluorocarbon surfactants, such as, for example, TritonTMX-100, ZonylTMFSO, FluoradTMFC-170C, and FluoradTMFC-171. These surfactants can be added individually or in combination of two or more thereof.
• the porous ink receiving layer comprises from 0.01 and 5 g/m of the surfactants, preferably from 0.05 and 1 g/m .
• dispersant agents, thickening agents, pH adjustor agents, lubricants, fluidity modifier agents, surface activators, waterproof agents, mold-releasing agents, whitening agents, ultraviolet absorbing agents, antioxidants can be added to the porous ink receiving layer.
• the support used in the ink-jet recording material of the invention includes any conventional support for ink jet recording sheet. As a support used in the invention, a transparent or opaque support can be used according to the final use of the ink jet recording sheet.
• any conventional support such as a film or plate of polyester resins, cellulose acetate resins, acryl resins, polycarbonate resins, polyvinyl chloride resins, poly(vinylacetals), poly ethers, polysulfonamides, polyamide resins, polyimide resins, cellophane or celluloid and a glass plate can be used in the present invention.
• the thickness of the transparent support is preferably from 10 to 200 mm.
• any conventional one such as paper, coat paper, synthetic paper, resin-covered paper, pigment-containing opaque film or foaming film can be used in the invention.
• the ink-jet recording material according to the present invention can be provided as a recording material having the same feeling to the touch, stiffness and texture as those of a usual photoprint. Further, the recording material according to the present invention becomes very close to the usual photoprint because its ink receiving layer has high surface gloss.
• the support may be subjected to a surface treatment such as a corona discharge treatment for improving its adhesiveness to the non-porous layer.
• a curl-preventing layer such as a resin layer or a pigment layer may be provided on the back surface of the support or at a desired position thereof to prevent curling.
• the non-porous layer is coated on the support and, in a successive step, the porous ink receiving layer can be coated on the non-porous layer to obtain an ink-jet recording material.
• a coating process to coat the non-porous layer to the support, and/or to coat the porous ink receiving layer to the non-porous layer a blade coating system, air-knife coating system, roll coating system, brush coating system, gravure coating system, bar coating, extrusion system, slide coater system, curtain coating system, or the like may be used.
• the extrusion system and slide coater system are particularly preferred to obtain by one pass a thick coating of proper and uniform thickness.
• a slide coater as described, for example, in US patent No.
• 2,761,419 is a multilayer die composed of a pack of elements, where distribution cavities are formed between each pair of elements. Coating liquids are laterally or centrally fed in the distribution cavities and uniformly spread through a slot, at which end they flow down an inclined plane, stacking in a multilayer stack. At the end of the slide, at a short distance from the edge (about 100-500 microns), the liquid meets and coats the moving web.
• a micro-porous ink-jet recording material was obtained by slide coating on the top of a 214g/m 2 resin coated paper support a micro-porous layer comprising, as dry coverage per square meters, 40g of DisperalTMHP14 (an alumina hydrate manufactured by Condea Gmbh, Hamburg, Germany), 4.67g of Airvol M 523 (a polyvinyl alcohol manufactured by Air Products, Allentown, Pennsylvania, having a saponification degree of 88 %, and a polymerization degree of 1,500), 1.3 lg of acetic acid, 0.6g of boric acid, 0.16g of TritonTMX-100 (a non-ionic surfactant available from Union Carbide Co., Danbury, Conn) and 0.029g of ZonylTMFSN-100 (a non-ionic fluorinated surfactant manufactured by DuPont Specialty Chemicals, Wilmington, Del.).
• DisperalTMHP14 an alumina hydrate manufactured by Condea Gmbh, Hamburg
• Sample 2 (comparison) was prepared as Sample 1 , but the micro-porous layer was applied on a non-porous layer previously coated onto the support, wherein the non-porous layer comprised 1.6 g/m 2 of a pig skin gelatin commercially available from SKW Biosystems, Boulogne Billancourt, France, 44 mg/m 2 of Triton 1 M X- 100 and the sulfuric salt of Compound A, available from Ciba Specialty Chemicals Inc, Basel, Switzerland as Ciba R Tinuvin R 292, in an amount corresponding to 1.9 g/m 2 of non salificated compound.
• the non-porous layer comprised 1.6 g/m 2 of a pig skin gelatin commercially available from SKW Biosystems, Boulogne Billancourt, France, 44 mg/m 2 of Triton 1 M X- 100 and the sulfuric salt of Compound A, available from Ciba Specialty Chemicals Inc, Basel, Switzerland as Ciba R Tinuvin R 29
• Sample 3 (comparison) was prepared as Sample 2, but the sulfuric salt of Compound A has been replaced by the sulfuric salt of Compound B, available from Ciba Specialty Chemicals Inc, Basel, Switzerland as Ciba R Tinuvin R 765, in the same amount.
• Sample 4 (comparison) was prepared as Sample 2, but the sulfuric salt of
• a solid image pattern including 7 patches was printed on the test sheet by a model Deskjet 970 ink-jet printer (manufactured by Hewlett-Packard Co., Palo Alto, California) with the original ink-jet cartridges made by Hewlett-Packard.
• the reflection density of recorded patches was measured for each single color cyan, magenta, yellow and for each component of the red, green, blue and black area with a densitometer, model TR 1224 (manufactured by Macbeth, a division of Kollmorgen Instrument Corp., Newburgh, New York).
• the patch area exhibiting a density near 1.00 was selected for each single color cyan, magenta and yellow; on the other hand, for the red, green and blue composite colors, it was considered each respective two components to choose the respective density 1.00 area; finally, the three components to choose the respective density 1.00 area were considered for the black composite color.
• the samples were submitted to a 2 Klux intensity fluorescent light exposure, at 50% relative humidity and 23 °C.
• the atmosphere air composition was maintained stable during all the test, in particular for the oxygen and H 2 S, SO 2 , NO 2 and O 3 gases present in little amounts in the ground.
• the recorded sample surface was maintained free of any physical protection to allow the natural air circulation. After incubation, the density was measured for each selected area in which an initial density near 1.00 had been measured; consequently, the air image resistance could be evaluated.
• Air image resistance evaluation was performed considering the rate of density lost calculated with the formula :
• Avg. Lost rate (%) [C+M+Y+(M red + Yred)+(C gre en + Ygreen)+(C b lue + M b l ue )+(C black + M black + Y black )]/12 with
• M i ack lost rate % of Magenta component in black area
• Sample 1 As shov/n in tables 1, the reference Sample 1, with no additives, presented a serious deterioration of the color with an average rate lost near to 50% of the initial optical density after 10 incubation weeks only.
• Samples 2 to 4 comprising hindered amine compounds different from the color fading inhibitor compounds used in the present invention due to the absence of hindered phenol moieties in their chemical structures, showed an unacceptable lost in density due to the degradation of colored matter.
• Sample 5 comprising compound (1) used in the present invention having hindered phenol and hindered amine moieties in its structure, showed a moderate average lost in density.

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