EP0046416B1 - Aufzeichnungsmaterial für Tintenstrahlaufzeichnung - Google Patents

Aufzeichnungsmaterial für Tintenstrahlaufzeichnung Download PDF

Info

Publication number
EP0046416B1
EP0046416B1 EP19810303806 EP81303806A EP0046416B1 EP 0046416 B1 EP0046416 B1 EP 0046416B1 EP 19810303806 EP19810303806 EP 19810303806 EP 81303806 A EP81303806 A EP 81303806A EP 0046416 B1 EP0046416 B1 EP 0046416B1
Authority
EP
European Patent Office
Prior art keywords
ink jet
recording sheet
jet recording
water
paper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19810303806
Other languages
English (en)
French (fr)
Other versions
EP0046416A3 (en
EP0046416A2 (de
Inventor
Mutsuaki Murakami
Yasutaka Hiromori
Hiroshi Naito
Yumiko Sekiguchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP11523680A external-priority patent/JPS5738185A/ja
Priority claimed from JP16497480A external-priority patent/JPS5787987A/ja
Priority claimed from JP16497580A external-priority patent/JPS5787988A/ja
Priority claimed from JP55164976A external-priority patent/JPS5787989A/ja
Priority claimed from JP55179766A external-priority patent/JPS57102391A/ja
Priority claimed from JP56007723A external-priority patent/JPS57120487A/ja
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Publication of EP0046416A2 publication Critical patent/EP0046416A2/de
Publication of EP0046416A3 publication Critical patent/EP0046416A3/en
Application granted granted Critical
Publication of EP0046416B1 publication Critical patent/EP0046416B1/de
Expired legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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

  • This invention relates to ink jet recording sheets.
  • Ink jet systems are of great interest because they offer reduced noise, ease of color recording, the possibility of high speed recording, and the utilization of ordinary papers. Such systems are now being used widely in facsimile and various other types of printers. It is generally accepted that some ordinary papers can be used as recording paper in ink jet recording systems but not all ordinary papers are satisfactory. In order to obtain copies of better quality, a recording sheet should meet various requirements as follows: (1) the paper should have excellent ink receptivity to allow ink dots deposited on the paper surface to be rapidly absorbed by the paper; and (2) the paper should not allow ink dots applied to a surface to run or spread.
  • Requirement (1) is the most fundamental one which must be met by ink jet recording papers and assumes great importance especially when color images are produced by the ink jet system. This is because in order to produce color images, it is necessary to make a variety of colors from combinations of yellow, cyan and magenta inks, so that inks of different colors are deposited on the same portion of paper surface, resulting in large amounts of ink per unit area.
  • Requirement (2) is necessary for obtaining clear recorded matters.
  • the optical density of recorded matter can be increased.
  • the simplest method of increasing the optical density of recorded matter is to increase the concentration of dye in ink.
  • this method has its limit because of the tendency of concentrated inks to clog a head nozzle. Accordingly, it is important that recording papers satisfy the above requirement.
  • recording papers should satisfy the following further requirements: (3) the degree of penetration of an ink in the direction of depth or in the longitudinal direction should not be too great; and (4) the paper should have excellent brightness.
  • the optical density of recorded matter largely depends on the state of the paper surface and if the degree of the penetration in the direction of depth is too great, it is difficult to make the optical density high.
  • the recording paper to be used in a ink jet recording system is generally made from bleached chemical pulp to which fillers, dyes and, if required, sizing agents and strength improvers are added.
  • Japanese Laid-open Patent Application No. 52-74340 discloses an ink jet recording paper which is characterized in that a ratio of an air resistance to basis weight (g/m 2 ) (air resistance/basis weight) is below 0.3 and that when an aqueous ink for ink jet recording is dropped in an amount of 0.004 ml, an absorption time of ink is in the range of from two seconds to 60 seconds. Further, Japanese Laid-open Patent Application No.
  • 52-53012 teaches a method of making recording papers which is characterized by applying a coating to a base paper which has been incorporated with a wet strength improver known per se and which has a Stockigt sizing degree of below 1 second whereby the resulting surface coated paper has a Stockigt sizing degree of below 3 seconds.
  • surface sizing agents including oxidized starch, PVA, galactomannon gum, polyacrylamide, sodium alginate, styrene-maleic acid copolymer, CMC and other cellulose derivatives, casein, soy bean protein and the like.
  • hydrophobic materials or latices, rosin and its derivatives petroleum resins, fumaric acid, maleic acid its derivative, waxes, synthetic resins, fatty acids, alkylketene dimers and the like, and, as pigment or filler, kaolin, calcium carbonate, aluminium hydroxide, satin white, titanium oxide, and urea-formalin organic fillers.
  • Japanese Laid-open Patent Application No. 55-5&30 a sheet for ink jet recording which comprises a support and an ink-receptive layer formed on the surface of the support, said sheet having an opacity of 55.0 to 97.5%, an absorptivity of the ink-receptive layer being in the range of 1.5 to 18.0 mm/min.
  • Japanese Laid-open Patent Application No. 55-5&30 a sheet for ink jet recording which comprises a support and an ink-receptive layer formed on the surface of the support, said sheet having an opacity of 55.0 to 97.5%, an absorptivity of the ink-receptive layer being in the range of 1.5 to 18.0 mm/min.
  • 55-11829 teaches a sheet for ink jet recording which has (1) two or more layers, (2) an opacity of 55.0 to 97.5%, (3) a top layer with a thickness of 1.0 to 16.0 pm, and (4) an ink-receptivity of the top layer of 1.5 to 5.5 mm/min and that of a second layer of 5.5 to 60.0 mm/min.
  • the ink-receptive layer of these sheets is formed of white pigments such as clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfide, satin white, aluminium silicate and lithopone.
  • binder resin there are mentioned oxidized starch, etherified starch, gelatin, casein, carboxymethyl cellulose, hydroxyethyl cellulose; polyvinyl alcohol and SBR latex.
  • IBM Technical Disclosure Bulletin, Volume 21, No. 6, November 1978, page 2502 describes an ink jet recording sheet comprising a paper support which has been rendered water-impenetrable, to prevent ink penetration, by coating with a dielectric or water-insoluble coating, by sizing or by beating, and a water-soluble layer on the water-impenetrable paper support of a polymer such as polyvinyl alcohol, starch, gelatine or polyvinyl pyrrolidone.
  • a polymer such as polyvinyl alcohol, starch, gelatine or polyvinyl pyrrolidone.
  • the present invention seeks to provide a jet recording sheet which shows an improved optical density, when recorded, over known sheets, which shows an excellent ink receptivity and is able to suppress ink dots from spreading, and which can ensure a certain extent of water-proofing and excellent fastness of light of recorded matter.
  • a recording sheet for ink jet recording which comprises a water-penetrable paper support to at least one surface of which has been applied an aqueous dispersion comprising, as binding agent, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer or a mixture thereof and a white filler, the weight ratio of said white filler to said binding agent being from 10:1 to 0.2:1, or which comprises a water-penetrable paper sheet prepared from a mixture of 100 parts by weight of a paper-making pulp and an aqueous dispersion comprising, as sizing agent, 2 to 20 parts by weight of polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer or a mixture thereof and 10 to 60 parts by weight of a white filler, the aqueous dispersion in each case comprising, as water-proofing agent, an aqueous emulsion-type resin or an alcohol-soluble
  • PVP polyvinylpyrrolidone
  • PVPNAc vinylpyrrolidone-vinyl acetate copolymer
  • the PVP and PVPNAc are water-soluble polymers and have a film-forming property. They are industrially applied as cosmetics, medical supplies, adhesives, cleaning agents and soaps, fiber-finishing agents, and inks, and also in the field of lithographic printing and paper.
  • PVP and PVP/ VAc which are applied in the field of the paper-making industry are used as a decoloring agent for rags for regeneration, an improver of cellulose paper to improve its tensile strength, and a binder for the specific type of paper made of inorganic flakes or fibers.
  • PVP When applied to inks making use of dyes, PVP renders the dye more readily soluble, serves to prevent gelation, and imparts deep color tone even to inks of low dye concentration.
  • PVP and PVPNAc are soluble in water and have generally an average molecular weight of several thousands to several hundred thousands. These polymers may be prepared by any known technique.
  • the commercially available vinylpyrrolidone and vinyl acetate copolymer has a ratio of PVNAc generally in the range of 70/30 to 30/70.
  • the PVP and/or PVA/VAc is used in the practice of the invention together with a white pigment or filler.
  • the filler which is preferably used in combination with the PVP resin or PVPNAc copolymer as will become apparent from examples appearing hereinafter include clay, talc, calcium carbonate, calcium sulfate, calcium silicate diatomaceous earth, magnesium silicate, terra alba, activated clay, magnesium oxide, magnesium carbonate and aluminium hydroxide.
  • fillers which are ordinarily employed in the paper-making industry such as titanium oxide, silica, aluminium silicate, satin white and zinc oxide may be used though they are inferior in optical density and other characteristics to those mentioned above.
  • an aqueous dispersion of the binding agent, the water-proofing agent and the filler is applied onto at least one surface of the paper support.
  • the weight ratio of the filler to the binding agent is generally 10:1 to 0.2:1, preferably 1:1 to 1:2. This will be particularly described in examples appearing hereinafter.
  • the aqueous dispersion is applied to a paper support, which may be any paper ordinarily employed for ink jet recording purpose, in an amount of 3 to 50,g/m 2 on the dry basis.
  • the coating amount is from 10 to 30 g/m 2 and most preferably about 20 g/ M 2 .
  • the PVP and/or PVPNAc binding agent resin may be mixed with a water-soluble sizing agent or binder which is ordinarily employed in the paper-making industry, including, for example, oxidized starch, PVA, styrene-maleic acid copolymer, carboxymethyl cellulose (CMC), and hydroxyethylcellulose.
  • a water-soluble sizing agent or binder which is ordinarily employed in the paper-making industry, including, for example, oxidized starch, PVA, styrene-maleic acid copolymer, carboxymethyl cellulose (CMC), and hydroxyethylcellulose.
  • the PVP and/or PVPNAc binding agent resin should be contained in an amount of not smaller than 20 wt% of the mixture.
  • plasticizers such as dimethyl phthalate, glycerine, diethylene glycol, sorbitol allyl- sulfonamide-formaldehyde, cellulose butyrate and cellulose butyrate-propionate.
  • the aqueous dispersion is mixed with stock pulp and then an ink i-at recording paper is made from the mixture by any known paper-making technique.
  • the paper incorporating therein the PVPNAc resin, the water-proofing agent and filler composition has several advantages: The making process is simple; and the PVP or PVPNAc is readily soluble in water and is thus poor in water proofing, so that when a PVP or PVPNAc-coated paper is dipped in water, the coating layer is readily dissolved out but the internally incorporated paper has a certain degree of water proofing though the filler comes off from the paper when dipped in water.
  • the internally applied recording paper can be made by one step without involving an additional coating process and is thus much simpler in manufacturing step than the surface-coated recording paper.
  • the resin and filler are usually present in amounts greater than those required for the surface coating technique. That is, as defined hereinbefore, the PVP and/or PVPNAc is used in an amount of 2 to 20 parts by weight and a white filler is used in an amount of 10 to 60 parts by weight both per 100 parts by weight of stock pulp.
  • the amount of the white filler of course, varies more or less depending on the type of the filler.
  • the water-proofing of either type of recording paper is much improved by the presence in the aqueous dispersion of, as water-proofing agent, the aqueous emulsion-type resin or a polymer soluble in alcohol which is capable of forming a water-proof film after drying.
  • Water-soluble resin binders such as oxidized starch, PVA, CMC and hydroxyethyl cellulose serve to improve the water-proofing as described hereinbefore when used in combination with PVP or PVPNAc but are not essential for such purpose.
  • the coating layer obtained from the mixture of a water-soluble resin binder and PVP or PVPNAc is dissolved in water in 10 to 15 seconds and an increasing amount of the water-soluble resin binder gives an adverse influence of ink receptivity.
  • aqueous emulsion useful in the practice of the invention are those of polyvinyl acetate, ethylene-vinyl acetate copolymer (having an ethylene content of below 30%), acrylic esters and water-soluble shellac.
  • polymers soluble in alcohol include polyvinyl butyral, polyacrylamide, polyamide-epichlorohydrin, shellac and polyvinyl acetate. These resins are capable of forming films of relatively good water proofing after drying. The amount of these resins is in the range of 1 to 50 wt%, preferably 2 to 20 wt%, of a mixture of the resin and PVP or PVPNAc.
  • various additives may be added to the PVP or PVPNAc and filler.
  • the resistance or the fastness to light of recorded matter is one of important problems to solve.
  • the light fastness of recorded matter can be improved by adding to the aqueous dispersion of PVP and/ or PVPNAc, water-proofing agent and filler (1) antioxidants, (2) UV absorbers and (3) metal oxides, metal chlorides or tannic acid capable of reacting with dyes to convert the dyes into light-fast dyes.
  • a magenta ink composed of 79% of water, 20% of ethylene glycol and 11 % of Basic Violet showed light resistance as follows.
  • UV absorbers were effective to prevent fading of recorded matter, which was experimentally found true.
  • antioxidants capable of converting dyes into light-resistant dyes or pigments are suitably used in amounts of 0.1 to 10 wt% of a mixture of the PVP or PVPNAc and filler.
  • dyes that can be employed in inks for use with the recording papers of the invention are C.I. Basic Yellow 11, C.I. Basic Red 1, C.I. Basic Red 3, C.I. Basic Violet 14, C.I. Basic Blue 3, C.I. Mordant Orange 4, C.I. Mordant Red 15, C.I. Mordant Violet 5, C.I. Mordant Black 7, C.I. Acid Yellow 17, C.I. Acid Orange 7, C.I. Acid Red 88, C.I. Acid Violet 49, C.I. Acid Blue 7, C.I.
  • Acid-Black 2 C.I. Acid Black 31, C.I. Basic Yellow 11, C.I. Basic Red 13, C.I. Basic Yellow 17, C.I. Direct Yellow 50 and C.I. Direct Red 80.
  • Inks containing these dyes can be composed of 76 or 77 to 79 percent by weight of water, 20 percent of ethylene glycol and 1 to 3 or 4 percent by weight of the dye.
  • the ink jet recording was carried out using an On-demand-type head with a diameter of nozzle of 40 ⁇ m in which three ink jetting heads were used to discharge therefrom different types of inks including cyan, yellow and magenta. By the combination of these inks, different colors of red, green, blue and sepia were made. The discharge of ink was changed in seven stages by controlling an application voltage and the recording of 6 lines/mm was conducted.
  • amounts of discharge per unit area in the respective stages are 2.6 x 10- 4 cc/cm 2 in first stage, 4.7 x 10- 4 cc/cm 2 in second stage, 6.4 x 10- 4 cc/ cm 2 in third stage, 7.0 x 10- 4 cc/cm 2 in fourth stage, 7.9 x 10- 4 cc/cm 2 in fifth stage, 8.7 x 10- 4 cc/cm 2 in sixth stage, and 9.4 x 10- 4 cc/cm 2 in seventh stage, respectively.
  • the amounts of discharge in the respective stages become double and in the case of sepia color, they become three times. Accordingly, the severest recording conditions are those for the sepia color in the seventh stage. Aside from these recordings, a recording of 2 lines/mm was also conducted for comparison.
  • Recorded matters were evaluated according to the following measurements or observations: (1) Measurement of optical density of the respective colors in the seventh stage; (2) Judgement of a stage of sepia color where inks start to run or spread so as to check a degree of the running or spreading of the inks (which show a degree of ink receptivity of paper); (3) Measurement of a time before the sepia color of the seventh stage is apparently dried after application thereof; and (4) Measurement of a rate of area of recorded matter of the first stage in which two lines/mm were recorded (to know a degree of spreading of ink dots or a degree of so-called sharpness).
  • calcium carbonate was used as a white pigment and different types of binder resins were used including PVP and PVPNAc to be used in the present invention.
  • each binder resin was added 15 wt% of calcium carbonate of a powder form having a size of 0.1 to 0.2 pm, followed by fan agitating to give a slurry.
  • This slurry was applied onto a commercially available groundwood paper by means of a wire bar, followed by roll pressing to obtain a surface-coated paper.
  • the coated paper had a thickness of 5 to 20 ⁇ m, i.e. 0.3-2.0 g of the coating was applied onto an A-4 size paper.
  • the binder resin gives a great influence on the characteristics of ink spreading, drying time and the like and the PVPNAc resins involve no spreading or running at the seventh stage and are thus much better than the other binder resins.
  • PVA and hydroxyethyl cellulose rank second to PVP and PVPNAc with respect to optical density but these resins were inferior in spreading characteristic, i.e. spreading occurred at the sixth stage, and required a drying time of as long as 60 to 80 seconds.
  • oxidized starch was excellent and PVP and PVP/ VAc showed such characteristics next to oxidized starch.
  • PVP and PVP/VAc were used as a binder resin and different types of white pigments were used in combination for comparative purpose.
  • Example 2 To a 10% aqueous solution of PVP or PVPNAc was added each of white pigments to be tested to give a slurry in the same manner as in Example 1 and the slurry was applied in the same manner as in Example 1 to obtain a surface coated paper.
  • the type and amount of white pigment and the results of recorded matter are shown in Table 2 below with regard to the PVP binder resin.
  • the white pigments showing no fading phenomenon are conveniently and preferably used.
  • Preferable pigments further include magnesium silicate, terra alba, activated clay, magnesium oxide and magnesium carbonate.
  • the spreading characteristic and drying time there is not a significant difference depending on the type of pigment, revealing that such characteristics are mainly dependent of the type of binder.
  • the binder used was PVP and similar results were obtained when PVP ⁇ IAc was used except that the optical density was reduced by about 0.5 in all the cases.
  • PVP was used as binder resin and calcium carbonate, calcium silicate and talc were used as pigment to determine an effect of a ratio by weight of the binder and the white pigment on the recording characteristics.
  • the coated paper was made in the same manner as in Example 1. In Table 3, there are shown results of a test using calcium carbonate.
  • a PVP/calcium carbonate (with an average size of 0.1 to 0.2 pm) ratio by weight is preferably in the range of 10:1 1 to 0.25:1.
  • a calcium silicate powder having an average particle size of 0.1 pm and a talc powder having an average size of 0.2 to 0.3 ⁇ m it was found that a preferable weight ratio was in the range of 10:1 to 0.5:1 for calcium silicate and 5:1 to 0.2:1 for talc.
  • the weight ratio is, of course, dependent on the size of white pigment and the weight ratio of PVP or PVPNAc and a white pigment is conveniently in the range of 10:1 to 0.2:1.
  • composition comprising calcium carbonate and PVP was applied in different thicknesses ranging from 4 pm to 28 ⁇ m, no significant difference in recording characteristics was found in this range of thicknesses.
  • the coated layer should preferably have a thickness of 8 ⁇ m or more, and the coating composition of the invention can be widely applied to a wide variety of paper supports.
  • binder resins such as PVA, oxidized starch and the like show better ink receptivity when used in combination with PVP.
  • PVP PVP
  • the content of PVP depends on the type of the second binder, it is in the range of over 20 wt% when the binder resin used in combination with PVP shows water absorptivity such as PVA and in the range of 33 wt% when the second binder resin shows no water absorptivity.
  • the characteristics of the recording papers made by the size press technique are substantially the same as those of the recording papers obtained by the wire bar.
  • the recording paper of the coated type using PVP/VAc as binder had an optical density of 0.99, a spreading stage of >7, a drying time of ⁇ 10, and a rate of area of ⁇ 10 as shown in Table 1, which are almost the same as those of Table 5.
  • the recording characteristics are almost the same as those of Table 4. Accordingly, the size press technique can be used similarly with the surface coating method.
  • resins used as sizing agents or binders and calcium carbonate used as white pigment were applied internally or mixed with pulp.
  • LBKP and NBKP were mixed in a ratio of 1:2 and beaten in a refiner. Then, light calcium carbonate was added to the pulp in an amount of 30 parts by weight per 100 parts by weight of the pulp and PVP or PVP/ VAc was added in an amount of ranging from 0.5 to 30 wt% based on the pulp.
  • the pulp composition was subjected to a paper-making process using a Fourdriner test machine to make a paper with a basis weight of 70 g/m 2 . The thus made papers were each subjected to the calender rolls to give recording papers.
  • the optical density is obtained from the magenta color of the seventh stage and as regards the other six colors, a similar tendency is observed.
  • the binder resin should be contained in an amount of at least 2% of the pulp. This is much larger as compared with an amount of an strength improver ordinarily employed in the paper-making industry (generally in the range of 0.2 to 1 wt%).
  • the recording papers in which 30% of PVP or PVPNAc based on the pulp is contained show excellent recording characteristics but become sticky to the touch. In addition, such papers show a blocking tendency.
  • the content of PVP or PVPNAc is in the range of 2 wt% to 20 wt% of the pulp.
  • an effective amount of calcium carbonate is in the range of 10 to 60 wt% of the pulp.
  • the content of calcium carbonate more or less depends on the content of PVP, e.g. when the content of PVP is 2%, the upper limit in content of calcium carbonate was found to be 40%. Similar results were obtained when PVPNAc was used instead of PVP.
  • white pigments in this internal application technique are aluminium hydroxide, silica, aluminium silicate, magnesium silicate, terra alba, activated clay, magnesium oxide, magnesium carbonate and aluminium oxide.
  • white pigments preferable ones are those mentioned with respect to the surface coating method.
  • binder resin made of 90 parts by weight of PVP and 10 parts by weight of different types of film-forming polymers were used.
  • the water proof was equated as follows: a time before the coated layer was completely separated from a coated paper specimen with a size of 1 cm x 2 cm after having immersed the coated paper vertically in water was measured. The test results are shown in Table 8 below.
  • PVP and/or PVPNAc are also usable in combination with PVP and/or PVPNAc including vinyl acetate-acrylonitrile copolymer, styrene resin, styrene-acrylonitrile copolymer, methacrylic ester resin, polyamide resin, melamine resin and melamine-urea resin.
  • Example 8 an influence of polyvinyl acetate in a binder resin composed of PVP and polyvinyl acetate was checked.
  • talc Choinese talc
  • the proof to water improves as the amount of polyvinyl acetate is increased.
  • the optical density, spreading characteristic and drying time become worse with an increasing amount of polyvinyl acetate.
  • a maximum amount of polyvinyl acetate should be 50%, i.e. it is necessary that polyvinyl acetate does not exceed that of PVP.
  • the binder system containing 2% of polyvinyl acetate does show little effect and thus polyvinyl acetate should be over 2%.
  • the characteristics of the recording papers made by the size press method are excellent similarly to those of the recording papers made by the wire bar coating method.
  • the recording papers made by the size press method are slightly superior to those obtained by the wire bar coating method.
  • the size press technique can be used similarly with the surface coating method.
  • the measurement of light resistance was conducted according to the method as prescribed in JIS L0843-71 using a 2.5 KW xenon fade meter of an air-cooling type (made by Suga Tester K.K.).
  • the irradiation energy was 464 J/cm 2 . Hr, which is 9.6 times that of an average sunlight and 380 times that of a fluorescent lamp.
  • the ink jet recording was carried out using an On-demand-type head having a nozzle diameter of 40 ⁇ m and a voltage of 200 V was applied to the recording system.
  • a discharge per unit area was 7.9 x 10- 4 cc/cm 2 .
  • Recording papers used were made by applying onto a commercially available high quality paper a coating composition comprising polyvinyl alcohol/polyvinylpyrrolidone (40/60) as binder and calcium carbonate as white filler in a binder-to-filler weight ratio of 1:1.
  • the coating amount was 40 g/m 2 .
  • Antioxidants, UV absorbers and the specific type of compounds capable of reacting with dyes were dissolved in the binder to make recording papers.
  • the additives remarkably improve the light resistance of recorded matter.
  • the phosphorus-containing acids are preferred because of their excellency in color retentivity.
  • Example 11 was repeated using various antioxidants, with the results shown in Table 13 below.
  • antioxidants can remarkably improve the light resistance.
  • the degree of improvement depends on the type of antioxidant, but hydroquinone, p-tert-butylcatechol, 2,6-di- tert-butylphenol and methylhydroquinone have been found to be particularly good in improving light resistance.
  • styrenated phenol 2,2'-methylene- bis(4-ethyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-thiobis(4-methyl-6-t-butylphenol), alkylthiodipropionates, 2-mercaptobenzoimidazole, N-n-butyl-p-aminophenol, phenylenediamines, a-naphthylamine, N-phenyl-a-naphthylamine, N,N'- disalicylidene-1,2-propylenediamine, phenothiazine, tris(nonylphenyl)phosphite, triphenylphosphite, tris(3,5-di-t-butyl
  • Example 11 was repeated using various UV absorbers, with the results shown in Table 14 below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Paper (AREA)

Claims (10)

1. Blattförmiges Aufzeichnungsmaterial für Tintenstrahlaufzeichnung, das aus einem wasserdurchlässigen Träger aus Papier besteht, wobei auf mindestens eine Oberfläche des Trägers eine wäßrige Dispersion aufgebracht worden ist, die Polyvinylpyrrolidon, Vinylpyrrolidon-Vinylacetat-Copolymer oder eine Mischung davon als Bindemittel und einen weißen Füllstoff enthält, und wobei das Masseverhältnis des erwähnten weißen Füllstoffs zu dem erwähnten Bindemittel 10:1 bis 0,2:1 beträgt, oder das aus einem wasserdurchlässigen Papierblatt besteht, das aus einer Mischung von 100 Masseteilen eines Papierrohstoffs und einer wäßrigen Dispersion, die 2 bis 20 Masseteile Polyvinylpyrrolidon, Vinylpyrrolidon-Vinylacetat-Copolymer oder einer Mischung davon als Leimungsmittel und 10 bis 60 Masseteile eines weißen Füllstoffs enthält, hergestellt wird, wobei die wäßrige Dispersion in jedem Fall als wasserdichtmachendes Mittel ein Harz vom Typ einer wäßrigen Emulsion oder ein alkohollösliches Harz, das beim Trocknen einen wasserdichten Film bildet, in einer auf die Gesamtmasse der als wasserdichtmachendes Mittel und der als Bindemittel oder Leimungsmittel verwendeten Harze bezogenen Menge von 1 bis 50 Masse% enthält.
2. Blattförmiges Aufzeichnungsmaterial für Tintenstrahlaufzeichnung nach Anspruch 1, bei dem die erwähnte Dispersion in einer Menge von 3 bis 50 g/m2 (Bezugsbasis Trockenmasse) auf eine Oberfläche des Trägers aus Papier aufgebracht worden ist.
3. Blattförmiges Aufzeichnungsmaterial für Tintenstrahlaufzeichnung nach Anspruch 1 oder 2, bei dem der erwähnte Füllstoff ein Pulver von Ton, Talk, Calciumcarbonat, Calciumsulfat, Calciumsilicat, Kieselgur, Magnesiumsilicat, Kaolin, aktiviertem Ton, Magnesiumoxid, Magnesiumcarbonat oder Aluminiumhydroxid ist.
4. Blattförmiges Aufzeichnungsmaterial für Tintenstrahlaufzeichnung nach Anspruch 1, 2 oder 3, bei dem die wäßrige Dispersion auch ein wasserlösliches Harz enthält, wobei das als Bindemittel oder Leimungsmittel verwendete Harz in einer auf die Gesamtmenge der erwähnten Harze bezogenen Menge von mindestens 20 Masse% verwendet wird.
5. Blattförmiges Aufzeichnungsmaterial für Tintenstrahlaufzeichnung nach einem der vorhergehenden Ansprüche, bei dem die wäßrige Dispersion ein Plastifizierungsmittel enthält, um die Härte eines Films zu steuern, der aus dem als Bindemittel oder Leimungsmittel verwendeten Harz gebildet wird.
6. Blattförmiges Aufzeichnungsmaterial für Tintenstrahlaufzeichnung nach einem der vorhergehenden Ansprüche, bei dem die wäßrige Dispersion 0,1 bis 10 Masse% eines Antioxidationsmittels, eines UV-Absorptionsmittels oder einer zum Reagieren mit einem Farbstoff befähigten Verbindung enthält.
7. Blattförmiges Aufzeichnungsmaterial für Tintenstrahlaufzeichnung nach Anspruch 6, bei dem das Antioxidationsmittel, das UV-Absorptionsmittel oder die zum Reagieren mit einem Farbstoff befähigte Verbindung mindestens in einer Oberflächenschicht des blattförmigen Aufzeichnungsmaterials enthalten ist.
8. Blattförmiges Aufzeichnungsmaterial für Tintenstrahlaufzeichnung nach Anspruch 6, bei dem das Antioxidationsmittel, das UV-Absorptionsmittel oder die zum Reagieren mit einem Farbstoff befähigte Verbindung in dem blattförmigen Aufzeichnungsmaterial enthalten ist.
9. Blattförmiges Aufzeichnungsmaterial für Tintenstrahlaufzeichnung nach Anspruch 6, 7 oder 8, bei dem die zum Reagieren mit einem Farbstoff befähigte Verbindung eine Wolframatophosphorsäure, eine Molybdatophosphorsäure oder eine Wolframatomolybdatophosphorsäure ist.
10. Blattförmiges Aufzeichnungsmaterial für Tintenstrahlaufzeichnung nach einem der vorhergehenden Ansprüche, bei dem das Masseverhältnis des erwähnten weißen Füllstoffs zu dem erwähnten Bindemittel 1:1 bis 2:1 beträgt.
EP19810303806 1980-08-20 1981-08-20 Aufzeichnungsmaterial für Tintenstrahlaufzeichnung Expired EP0046416B1 (de)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP11523680A JPS5738185A (en) 1980-08-20 1980-08-20 Ink jet recording paper
JP115236/80 1980-08-20
JP16497480A JPS5787987A (en) 1980-11-21 1980-11-21 Ink jet recording sheet
JP16497580A JPS5787988A (en) 1980-11-21 1980-11-21 Ink jet recording paper
JP55164976A JPS5787989A (en) 1980-11-21 1980-11-21 Ink jet recording paper
JP164976/80 1980-11-21
JP164974/80 1980-11-21
JP164975/80 1980-11-21
JP179766/80 1980-12-18
JP55179766A JPS57102391A (en) 1980-12-18 1980-12-18 Ink jet recording sheet
JP7723/81 1981-01-20
JP56007723A JPS57120487A (en) 1981-01-20 1981-01-20 Ink jet recording paper

Publications (3)

Publication Number Publication Date
EP0046416A2 EP0046416A2 (de) 1982-02-24
EP0046416A3 EP0046416A3 (en) 1982-12-08
EP0046416B1 true EP0046416B1 (de) 1986-11-12

Family

ID=27548077

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19810303806 Expired EP0046416B1 (de) 1980-08-20 1981-08-20 Aufzeichnungsmaterial für Tintenstrahlaufzeichnung

Country Status (3)

Country Link
EP (1) EP0046416B1 (de)
CA (1) CA1186574A (de)
DE (1) DE3175592D1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008110661A1 (en) * 2007-02-05 2008-09-18 Upm-Kymmene Oyj A method for making printing paper and a mixture composition

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4542059A (en) * 1982-08-23 1985-09-17 Canon Kabushiki Kaisha Recording medium
US4503111A (en) * 1983-05-09 1985-03-05 Tektronix, Inc. Hydrophobic substrate with coating receptive to inks
US4636409A (en) * 1983-09-19 1987-01-13 Canon Kabushiki Kaisha Recording medium
JPS60198285A (ja) * 1984-03-23 1985-10-07 Ricoh Co Ltd インクジエツト記録材
US4642247A (en) * 1984-06-29 1987-02-10 Canon Kabushiki Kaisha Recording medium
US4664952A (en) * 1984-10-23 1987-05-12 Canon Kabushiki Kaisha Recording medium and recording method utilizing the same
CA1316957C (en) * 1986-12-18 1993-04-27 John Brian Cooper Pressure sensitive record material
GB8706634D0 (en) * 1987-03-20 1987-04-23 Ecc Int Ltd Paper coating
JPH0720727B2 (ja) * 1987-10-08 1995-03-08 新王子製紙株式会社 インクジェット記録用塗工シ−ト
DE69700228T2 (de) 1997-03-20 1999-12-16 Ilford Imaging Ch Gmbh Aufzeichnungsblatt für das Tintenstrahldruckverfahren
KR100625273B1 (ko) * 1998-10-21 2006-09-18 가부시키가이샤 도모에가와 세이시쇼 잉크젯 프린터 기록용 매체
DE60010542T2 (de) * 1999-02-16 2005-05-12 Oji Paper Co., Ltd. Tintenstrahlaufzeichnungsmaterial mit verbesserter Lichtechtheit

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3793075A (en) * 1971-12-20 1974-02-19 Moore Business Forms Inc Dialkyl tartrate-heteropolyacid developing system for dye precursor compounds
DE2234823C3 (de) * 1972-07-15 1984-06-20 Agfa-Gevaert Ag, 5090 Leverkusen Aufzeichnungsmaterial für Ink-Jet-Bilder
FR2264129B1 (de) * 1974-03-14 1978-07-28 Rhone Poulenc Ind
DE2529512C2 (de) * 1975-07-02 1984-10-04 Henkel KGaA, 4000 Düsseldorf Klebmittel auf Basis von wäßrigen Dispersionen von Copolymerisaten des Butadiens
JPS555830A (en) * 1978-06-28 1980-01-17 Fuji Photo Film Co Ltd Ink jet type recording sheet
JPS55146786A (en) * 1979-05-02 1980-11-15 Fuji Photo Film Co Ltd Ink-jet recording sheet

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008110661A1 (en) * 2007-02-05 2008-09-18 Upm-Kymmene Oyj A method for making printing paper and a mixture composition

Also Published As

Publication number Publication date
EP0046416A3 (en) 1982-12-08
DE3175592D1 (en) 1987-01-02
EP0046416A2 (de) 1982-02-24
CA1186574A (en) 1985-05-07

Similar Documents

Publication Publication Date Title
US4425405A (en) Ink jet recording sheet
DE69014001T2 (de) Aufnahmemittel und dabei verwendete Aufnahmemethode.
DE69310107T3 (de) Aufzeichnungsblatt für Tintenstrahlschreiber und Verfahren zu seiner Herstellung
US5851651A (en) Coating for inkjet recording
EP1081197B1 (de) Papier für die Tintenstrahlaufzeichnung, gemahlenes ausgefälltes Kalziumkarbonatpigment enthaltend
EP0046416B1 (de) Aufzeichnungsmaterial für Tintenstrahlaufzeichnung
EP0947348B1 (de) Aufzeichnungsmedium und Tintenstrahlaufzeichnungsverfahren damit
DE19505295C2 (de) Tintenstrahl-Aufzeichnungsblatt
JPH0321356B2 (de)
EP1126081B1 (de) Schichtträger für Aufzeichnungsschichten
DE3707627A1 (de) Aufzeichnungsblatt fuer tintenstrahldrucker
DE60012254T2 (de) Tintenstrahlaufzeichnungsmedium
US5919558A (en) Inkjet recording sheet
DE60205227T2 (de) Tintenstrahldruckpapier, das ein aminderivat des polyvinylalkohols enthält
DE69920218T2 (de) Tintenstrahlaufzeichnungspapier
JPS60109894A (ja) インクジェット記録用紙
EP2076398A1 (de) Ink-jet-aufzeichnungsmaterial mit perforierter rückseitenkunstharzschicht
JPH0234793B2 (de)
JPS6218355B2 (de)
JPH0119352B2 (de)
KR100255041B1 (ko) 칼라잉크젯용용지의제조방법
JP2006181954A (ja) インクジェット記録用紙
JP3299723B2 (ja) インクジェット記録用媒体
JP3074743B2 (ja) インクジェット記録用紙
JP2834782B2 (ja) 塗被紙の製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19811029

AK Designated contracting states

Designated state(s): DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): DE FR GB

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 3175592

Country of ref document: DE

Date of ref document: 19870102

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19940809

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19940810

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940823

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19950820

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19950820

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST