EP0728594B1 - Papier d'enregistrement - Google Patents

Papier d'enregistrement Download PDF

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Publication number
EP0728594B1
EP0728594B1 EP19960301013 EP96301013A EP0728594B1 EP 0728594 B1 EP0728594 B1 EP 0728594B1 EP 19960301013 EP19960301013 EP 19960301013 EP 96301013 A EP96301013 A EP 96301013A EP 0728594 B1 EP0728594 B1 EP 0728594B1
Authority
EP
European Patent Office
Prior art keywords
recording paper
ink
pigment
specific surface
surface area
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 - Lifetime
Application number
EP19960301013
Other languages
German (de)
English (en)
Other versions
EP0728594A1 (fr
Inventor
Yoshihiro c/o Res. Dev. Lab. of Prod. Kuroyama
Teiichi c/o Res. Dev. Lab. of Prod. Ohtani
Takashi c/o Res. Dev. Lab. of Prod. Ueno
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.)
Nippon Paper Industries Co Ltd
Original Assignee
Nippon Paper Industries Co Ltd
Jujo Paper 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
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Application filed by Nippon Paper Industries Co Ltd, Jujo Paper Co Ltd filed Critical Nippon Paper Industries Co Ltd
Publication of EP0728594A1 publication Critical patent/EP0728594A1/fr
Application granted granted Critical
Publication of EP0728594B1 publication Critical patent/EP0728594B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • 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
    • 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 relates to an ink jet recording material for recording with water-base ink and, more particularly to, an ink jet recording material which has suitability for full color printing and excellent ink absorptiveness.
  • ink jet recording fine ink drops ejected by a wide variety of mechanisms are made to adhere to a recording material to form a dot image thereon.
  • the ink jet recording is noiseless, and enables easy formation of full color images and high-speed printing.
  • the ink used for ink jet recording is usually water-base ink using a direct dye or an acid dye. Therefore, it has poor drying properties.
  • the paper used in the ink jet recording system is required to have the following properties of:
  • the ink volume is much greater because of overlap of many ink drops, and so rapid absorption of ink becomes difficult in such a region; as a result, a blurring phenomenon tends to occur.
  • the coated paper-type recording paper having its Stökigt sizing degree in the specified range, in Japanese Tokkai Sho 52-53012; the recording paper having at least two coats of a synthetic silica-containing coating material to increase its coverage rate, in Japanese Tokkai Sho 57-107879; the recording paper provided with the coated layer having a special void structure, in Japanese Tokkai Sho 58-110287; the recording paper provided with the coated layer cracked into many sections having a specified size, in Japanese Tokkai Sho 58-119888; and the recording papers using pigments having specific surface areas defined by BET method in the ranges specified respectively, in Japanese Tokkai Sho 60-174684 and 60-204390.
  • the Inventors have made intensive studies, and found that the ink jet recording suitability of a recording paper, especially an ink absorbing capacity thereof, is affected definitely by the quantity of ink passing through vacant spaces in the recording layer and this quantity correlates with the flow rate of a gas passing through a pigment-filled layer, and further that the recording paper having a particular relation between the specific surface area of a pigment present in the recording layer and the thickness of the recording layer can have not only high ink-absorbing capacity but also be free from a print-through phenomenon and have a properly controlled dot diameter, thereby achieving the present invention.
  • a recording paper having on one side of a base paper a recording layer comprising at least a pigment and a water-base binder, wherein the specific surface area of the pigment, Sw, determined at the voids ⁇ of 0.8 by the constant-pressure air permeability method and the thickness of the recording layer, L, satisfy the following relation: 5 ⁇ 10 -4 ⁇ Sw 2 ⁇ L ⁇ 2 ⁇ 10 -2 (m 5 /g 2 )
  • the recording paper prepared in accordance with the present invention is well suited for ink jet recording with water-base ink. Especially in full-color printing, the present recording paper can provide full-color images of high quality because it has excellent ink absorbing properties to achieve a small dot diameter and high optical density.
  • the recording layer having ink jet suitability is rich in vacant spaces, so it can be regarded as an aggregate of capillaries.
  • the factors variable in a recording layer are ⁇ , ⁇ , Sw and L.
  • ⁇ and ⁇ are numerical values depending on a pigment present in the layer, but their individual variable ranges are around 20 % at the most.
  • Sw and L each have a much wider variable range, or the variable range of the order of about 1,000 %. Accordingly, the ink absorbing capability of a recording layer can be approximately expressed by the terms of Sw 2 and L.
  • Sw is essentially the specific surface area of the pigment present in a recording layer, which is to be determined using ink, it has now been proved that Sw can satisfactorily be expressed by the specific surface area determined by the so-called constant-pressure air permeability method.
  • the specific surface area according to the constant-pressure air permeability method can be measured with an apparatus for measuring the specific surface area of a powder, e.g., Model SS-100, made by Shimazu Seisakusho Ltd.
  • the specific surface area of the sample is difficult to be determined at the prescribed voids.
  • the specific surface area at the prescribed voids can be determined by interpolation or extrapolation.
  • the recording layer thickness L can be arbitrarily set up so far as the value Sw 2 ⁇ L is in the range 5 ⁇ 10 -4 -2 ⁇ 10 -2 m 5 /g 2 , preferably 1 ⁇ 10 -3 -1 ⁇ 10 -2 m 5 /g 2 .
  • the thickness L is preferably in the range of the order of 5-25 ⁇ m, wherein the recording layer can cover the surface of a base paper and sufficient print density can be secured.
  • the layer thickness can be determined with electron microphotographs of cross sections of the recording paper.
  • the pigment used in the present recording layer has no particular restrictions so far as its specific surface area Sw is in the range 8-30 m 2 /g, preferably 15-25 m 2 /g, when determined by the constant-pressure air permeability method.
  • synthetic silica such as amorphous silica or the like.
  • silica as used in the present invention is intended to include those defined in Kagaku Binran Oyo Kagaku Hen (which means “Handbook of Chemistry, Applied Chemistry Edition"), at page 256 (compiled by the Japanese Chemical Society, published by Maruzen in October 15, 1986), namely silica gel, white carbon, anhydrous silica and so on. In the present invention, it is especially desirable to use white carbon.
  • the specific surface area determined by the constant-pressure air permeability method in the present invention has no particular correlation with the specific surface area determined by the BET method. This is demonstrated by the data set forth in Table 1.
  • the binder used in a recording layer of the present recording paper has no particular restrictions, except that it is required to be a water-base binder.
  • Suitable examples of such a binder include starches such as oxidized starch, esterified starch, etc., cellulose derivatives such as carboxymethyl cellulose, etc., polyvinyl alcohol and the derivatives thereof, polyvinyl pyrrolidone, casein, gelatin, soybean protein, a styrene-acrylic resin and the derivatives thereof, a styrene-butadiene latex, an acrylic emulsion and a vinyl acetate emulsion.
  • the coating composition for the present recording layer it is desirable to admix a high solid-content emulsion from the standpoint of increasing the workability upon coating operation. Further, for the purpose of controlling the dot diameter, it is more desirable to use a styrene-butadiene latex as one constituent of the binder, and that in combination with at least one other constituent binder.
  • the constituent binder(s) combined therein may be those selected from the binders cited above.
  • the proportion of total constituent binders mixed with a pigment is preferably from 10 to 100 parts by weight per 100 parts by weight of the pigment.
  • the optimum value thereof varies within the limits defined above depending on the specific surface area of the pigment used.
  • the binder proportion is not necessarily limited to the foregoing range. In other words, the proportions beyond the foregoing limits are also allowable, provided that sufficient binding is ensured to the pigment and a porous structure appropriate for ink absorption is not broken.
  • the coating composition used in the present invention is prepared as a water-base composition comprising at least the pigment and the binder as described above.
  • a pigment dispersing agent a water holding agent, a thickener, an antifoaming agent, antiseptics, a coloring agent, a water resistance providing agent, a wetting agent, a fluorescent dye, an ultraviolet absorbent, an cationic polyelectrolyte and so on.
  • the method using a known coating machine can be adopted.
  • a coating machine mention may be made of a blade coater, an air knife coater, a roll coater, a brush coater, a kiss coater, a squeeze coater, a curtain coater, a bar coater, a gravure coater, a comma coater and so on.
  • composition coated can be dried by not only an usual ventilation method but also the drying method in which the coating is pressed against a heated mirror-finished surface while it is still wet, such as cast methods including the so-called direct cast method, re-wetting cast method and coagulation cast method.
  • Dots are printed with cyan ink, and reflection densities of 5 dots arbitrarily selected among them are measured with Konica Microdensitometer, PDM-5 (trade name, a product of Konica Co., Ltd.). The dot density is shown as the average of these 5 measurements.
  • Dots are printed with cyan ink, and diameters of 10 dots arbitrarily selected among them are measured with Image Analyzer (trade name, a product of ADS K.K.). The dot diameter is shown as the average of these 10 measurements.
  • the cross sections of the recording paper samples are observed with an electron microscope, and thereby the average coating thickness is determined.
  • Coatability, dryability and so on are synthetically judged, with those in Example 5 being taken as standards.
  • the pigment dispersion thus obtained was admixed with a solution prepared by dissolving 30 parts by weight of styrene-butadiene latex (Naugatex SN-307, trade name, a product of Sumitomo Daw Co. Ltd.) and 40 parts by weight of polyvinyl alcohol (PVA 105, trade name, a product of Kuraray Co., Ltd.) in 530 parts by weight of water to prepare a coating composition.
  • the coating composition thus obtained was coated on the aforementioned raw paper by means of a roll coater, and dried.
  • the thus prepared ink jet recording paper had a coating thickness of 10. ⁇ m.
  • the evaluation results thereof are set forth in Table 2.
  • An ink jet recording paper was prepared in the same manner as in Example 1, except that Synthetic Silica G (shown in Table 1) was used as pigment instead of Synthetic Silica D and the coating thickness was changed to 7 ⁇ m.
  • Synthetic Silica G shown in Table 1
  • the evaluation results thereof are also set forth in Table 2.
  • An ink jet recording paper was prepared in the same manner as in Example 1, except that Synthetic Silica E (shown in Table 1) was used as pigment, the styrene-butadiene latex content was reduced to 25 parts by weight and the coating thickness was changed to 22 ⁇ m.
  • Synthetic Silica E shown in Table 1
  • the evaluation results thereof are also set forth in Table 2.
  • An ink jet recording paper was prepared in the same manner as in Example 1, except that the styrene-butadiene latex content was reduced to 15 parts by weight.
  • the evaluation results thereof are also set forth in Table 2.
  • An ink jet recording paper was prepared in the same manner as in Example 1, except that Synthetic Silica F (shown in Table 1) was used as pigment, the polyvinyl alcohol content was increased to 45 parts by weight and the styrene-butadiene latex was not used, and the coating thickness was changed to 18 ⁇ m.
  • Synthetic Silica F shown in Table 1
  • An ink jet recording paper was prepared in the same manner as in Example 1, except that Synthetic Silica A (shown in Table 1) was used as pigment and the coating thickness was changed to 7 ⁇ m.
  • the evaluation results thereof are also set forth in Table 2.
  • An ink jet recording paper was prepared in the same manner as in Example 1, except that Synthetic Silica G (shown in Table 1) was used as pigment and the coating thickness was changed to 3 ⁇ m.
  • the evaluation results thereof are also set forth in Table 2.
  • An ink jet recording paper was prepared in the same manner as in Example 1, except that Synthetic Silica H (shown in Table 1) was used as pigment, the styrene-butadiene latex content was reduced to 25 parts by weight and the coating thickness was changed to 25 ⁇ m.
  • Synthetic Silica H shown in Table 1
  • the evaluation results thereof are also set forth in Table 2.
  • An ink jet recording paper was prepared in the same manner as in comparative example 1, except that 25 parts by weight of a vinyl acetate-ethylene copolymer emulsion (Sumicaflex 470, trade name, a product of Sumitomo Chemical Co., Ltd.) was used instead of 30 parts by weight of the styrene-butadiene latex and the coating thickness was changed to 5 ⁇ m.
  • the evaluation results thereof are also set forth in Table 2.
  • the ink jet recording papers according to the present invention those prepared in Examples 1 to 5, showed complete absorption of ink and provided prints which were high in dot density, small in dot diameter and free from print through.
  • the ink jet recording papers beyond the scope of the present invention those prepared in Comparative Examples 1, 2 and 4, were inferior in most of the properties exmined, and the ink jet recording paper prepared in Comparative Example 3 was inferior in dot density although it had satisfactory ink absorbing capacity.

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

Claims (9)

  1. Papier d'enregistrement ayant, sur un côté d'un papier de base, une couche d'enregistrement contenant au moins un pigment et un liant à base d'eau, dans lequel la surface spécifique du pigment, Sw, déterminée pour un taux de vides ε de 0,8 par la méthode de la perméabilité à l'air sous pression constante et l'épaisseur de la couche d'enregistrement, L, satisfont la relation suivante : 5 × 10-4 ≤Sw2 × L≤ 2 × 10-2 (m5/g2)
  2. Papier d'enregistrement selon la revendication 1, dans lequel la surface spécifique du pigment est dans la plage suivante : 8 ≤ Sw ≤ 30 (m2/g)
  3. Papier d'enregistrement selon la revendication 1 ou la revendication 2, dans lequel le liant à base d'eau comprend au moins deux constituants, dont l'un est un latex styrène-butadiène.
  4. Papier d'enregistrement selon l'une des revendications 1 à 3, dans lequel le pigment est une silice synthétique.
  5. Papier d'enregistrement selon l'une des revendications 1 à 4, dans lequel la valeur de Sw2XL est comprise entre 1X10-3 et 1X10-2 m5/g2.
  6. Papier d'enregistrement selon l'une des revendications 1 à 5, dans lequel l'épaisseur L est comprise entre 5 et 25 µm.
  7. Papier d'enregistrement selon l'une des revendications 1 à 6, dans lequel la proportion du liant est comprise entre 10 et 100 parties en poids pour 100 parties en poids du pigment.
  8. Papier d'enregistrement selon la revendication 2, ou l'une quelconque des revendications 3 à 7 rattachée à celle-ci, dans lequel la surface spécifique Sw est comprise entre 15 et 25 m2/g.
  9. Papier d'enregistrement selon la revendication 4, ou l'une quelconque des revendications 5 à 8 ratachée à celle-ci, dans lequel la silice synthétique est le carbone blanc.
EP19960301013 1995-02-16 1996-02-14 Papier d'enregistrement Expired - Lifetime EP0728594B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP5183695 1995-02-16
JP7051836A JP3017653B2 (ja) 1995-02-16 1995-02-16 記録用紙及びその製造方法
JP51836/95 1995-02-16

Publications (2)

Publication Number Publication Date
EP0728594A1 EP0728594A1 (fr) 1996-08-28
EP0728594B1 true EP0728594B1 (fr) 1999-06-30

Family

ID=12897953

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19960301013 Expired - Lifetime EP0728594B1 (fr) 1995-02-16 1996-02-14 Papier d'enregistrement

Country Status (4)

Country Link
EP (1) EP0728594B1 (fr)
JP (1) JP3017653B2 (fr)
DE (1) DE69603036T2 (fr)
FI (1) FI960680A (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000041889A1 (fr) * 1999-01-12 2000-07-20 Imperial Chemical Industries Plc Support recepteur d'impression a jet d'encre

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58110287A (ja) * 1981-12-24 1983-06-30 Mitsubishi Paper Mills Ltd 記録用シ−ト
US5013603A (en) * 1986-06-13 1991-05-07 Mizusawa Industrial Chemicals, Ltd. Ink jet recording paper with amorphous silica filler
JP2927377B2 (ja) * 1992-08-07 1999-07-28 日本製紙株式会社 インクジェット記録用紙及びその製造方法

Also Published As

Publication number Publication date
JPH08216506A (ja) 1996-08-27
FI960680A0 (fi) 1996-02-15
DE69603036D1 (de) 1999-08-05
FI960680A (fi) 1996-08-17
JP3017653B2 (ja) 2000-03-13
EP0728594A1 (fr) 1996-08-28
DE69603036T2 (de) 1999-12-09

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