WO1986005448A1 - Feuille revelatrice de couleurs pour materiaux d'enregistrement d'images - Google Patents

Feuille revelatrice de couleurs pour materiaux d'enregistrement d'images Download PDF

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Publication number
WO1986005448A1
WO1986005448A1 PCT/JP1986/000135 JP8600135W WO8605448A1 WO 1986005448 A1 WO1986005448 A1 WO 1986005448A1 JP 8600135 W JP8600135 W JP 8600135W WO 8605448 A1 WO8605448 A1 WO 8605448A1
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WO
WIPO (PCT)
Prior art keywords
color
developer
image recording
parts
electron
Prior art date
Application number
PCT/JP1986/000135
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English (en)
Japanese (ja)
Inventor
Takahiro Torii
Original Assignee
Mitsubishi Paper Mills, 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
Application filed by Mitsubishi Paper Mills, Ltd. filed Critical Mitsubishi Paper Mills, Ltd.
Publication of WO1986005448A1 publication Critical patent/WO1986005448A1/fr

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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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders

Definitions

  • the present invention relates to a color developing system for image recording materials.
  • the nokerpon pressure-sensitive recording material basically consists of a colorless (loico) dye donor sheet (upper sheet) and a color development sheet (lower sheet) (in addition to this).
  • Some of the upper and lower gauze have a medium-use cane in the mouth, some applied products such as a self-contained cane), and a colorless (loico) dye is dissolved in a high boiling point solvent. In many cases, it is built into the power bus.
  • Micro-encapsulation is more conventional than the coacervation method, In-situ polymerization, interfacial polymerization, etc. are used.
  • colorless (roico) dyes crystalline dyes, 3, 3-(P-Dimethylamminephenyl) Naphtalide, 3-(P-Dimethylamminephenyl)-3-(2-Methylindol- 3-ILL)-6-REAL REAL METAL TAILIDE, such as dimethyl methylamine, benzil, vinyl, vinyl, vinyl Acrylic derivatives such as paroyl, 3-Diethylamino-6-methyl-7-chlorofluoroamine, 3-diethylamino-7-dibenzylamino MINOL FULL ORANGLE, 3-JETHYL AMINO-6-METHYL-7-ANNILINO FULL ORAN, 3-METHYL-CYCLOHEXIL -Methyl-7-aniline full-orange, 3-Ethyl-p-U-lilyamino- 6-methyl- 7-
  • High boiling point solvents which are often used for pressure sensitive recording materials, are alkylnaphthalene compounds represented by diisopropy lnaphthalene, 1-frone.
  • Ene-1-Jaryl alkanes typified by xylylene, alkyrbi phenyl alkenyl typified by isopropyl biphenyl, Aromatic hydrocarbons such as polyarylmethanes, alkylbenzenes, benzilnaphthalene diarylalkylenes, arylindines, etc .; Carboxylic acid ester compounds represented by dibutyl tartrate, dialkyl maleic acid, etc .: Phosphoric acid represented by acrylic acid phosphate Ester compound: castor Naturally occurring animal and vegetable oils and fats or modified products thereof such as silicone oil, soybean oil, cottonseed oil, and hake oil: high-boiling fractions of natural products such as mineral oil (which are derived from aliphatic hydrocarbons).
  • the electron-accepting color developer is an acidic white clay, which is an inorganic white colorant, a natural clay mineral such as atapargai, clay, and a monilironite-based clay mineral.
  • an inorganic acid such as nitric acid, sulfuric acid, etc. at a moderate or moderate degree.
  • C-type phenolic resins, aromatic carboxylic acids, and their polyvalent metal salts have already been proposed and used.
  • the organic developer, the novolak type phenolic resin, the substituted salicylic acid, which is an aromatic carboxylic acid, and the acid (salt) are as follows.
  • these acid compounds are naturally filled with synthetic mineral fine sand, hard glass fine particles, metal fine particles, etc.
  • a coating solution with a binder such as dextran, dextran, carboxymethyl acetylcellulose, or polyvinyl alcohol.
  • the developed coating solution obtained by applying the prepared coating solution to the sheet-shaped support has good smoothness, high color development degree, and excellent daylight resistance of the developed image.
  • the color development speed is slow, and the color image is discolored when it comes into contact with plastics plastics or oils.
  • the printability of the upper ink set, etc. is poor, and it is a synthetic product of Yuri Chemical. Therefore, it becomes a cost
  • the inorganic type developers have excellent printability such as ink-inking property and are inexpensive, so they are attractive as industrial materials, but the smoothness of the color developing system is poor.
  • stains smudge
  • One of the causes is that the particle size of the inorganic developer is large.
  • Activated clay which is a type of inorganic color developer, is described in Japanese Patent Publication No. 4 1-2 3 7 3
  • acid clay or similar clays are treated with mineral acid to dissolve the acid-soluble clay. Aluminium, iron, sodium zinc, zinc, and other basic components were eluted, washed with water and dried, and the particle size of 10 S clones or less obtained with formula powder was 80 weight parts. Particles with a size of more than 1 centimeter and less than 1 micron are generally used with a particle size of about 15 weight percent or less.
  • the particle size of the intimate-type developer should be adjusted so that the particle size of 5 micron or less becomes ⁇ 0 0 weight weight.
  • the specific surface area is also increased to 200 m fc / 3, and at the same time, the viscosity at the time of preparing the coating solution increases and the amount of the binder must be increased. Since the blanket of the printing machine is dirty, it is not very viable.
  • an object of the present invention is to provide a color-developing sheet for an image recording material which has improved smoothness, is free from stains (smudge), and is also excellent in printing suitability. It is in .
  • the above-mentioned purpose is to provide a color-forming sheet comprising an electron-accepting color developer, which can develop an electron-donating colorless dye, on the support, and an electron-donating colorless dye layer on the support.
  • a color-removing sheet for image recording material used in combination with a pigment a coating containing an inorganic developer and acrylic latex as the developer layer described above. Achieved by using layers.
  • the color developer that is particularly recommended is proposed in Japanese Patent Laid-Open No. 5-7 — 1 5 9 9 6 and Zhou 5 8 — 1 6 8 8 5
  • This is a clay mineral having a layered structure consisting of silica tetrahedrons, with a S i 0 2 content of 8 2 to 9 6.5 weight parts by weight on a dry basis (10 5 dried at 3 o'clock straw).
  • the acid treatment of the clay mineral is carried out to give a weight percentage of 85 to 95% by weight, and the clay mineral obtained is at least partially soluble in the medium in an aqueous medium.
  • Acid and / or aluminum compounds to form hydroxides when these soluble compounds are other than hydroxides are other than hydroxides.
  • Magnesium and Z in treated clay minerals Alternatively, it is called a semi-synthetic solid acid in Meisho, which is a new type of inorganic color developer produced by introducing an aluminum component and drying it as desired. And That is, this developer has a novel manufacturing method, and when the acid-treated clay ore is measured by X-ray diffraction or electron beam diffraction, it shows the silicic acid strength of the clay ore before acid treatment. It has a structure that does not substantially show a diffraction pattern based on a layered crystal composed of a tetrahedron.
  • the above-mentioned acid-treated clay minerals containing the above-mentioned magnesium and / or aluminum components were analyzed by electron beam diffraction to obtain a layered crystal composed of tetrahedral tetrahedrons.
  • the diffraction pattern based on X-ray diffraction does not show the diffraction pattern based on the crystal of the above-mentioned hierarchal structure, and at least the case of elements other than oxygen is shown. Contains elemental and magnesium and / or aluminum.
  • the insufficient coloring density which is the weak point of conventional clay mineral type developers represented by acid clay and activated clay, and the coloring image under high humidity can be obtained. It is possible to renew the decrease in concentration.
  • the present inventors have prepared a developer series by preparing a semi-synthetic solid acid, which is an inorganic developer and a new type of color developer manufactured as described above, into a coating liquid.
  • a semi-synthetic solid acid which is an inorganic developer and a new type of color developer manufactured as described above.
  • the degree of color development is certainly high, and the deterioration of the degree of dryness of the color image under high humidity is improved, but on the other hand, the drawback is that the smoothness is not as good as that of conventional activated clay.
  • stains smudge
  • semi-synthetic solid contacts which are a type of slush-free developer
  • a semi-synthetic solid acid which is a color developer
  • an acrylic latex which is a binder
  • the color development system of the present invention has high smoothness, has very little stain (smudge), has a high color density, and is free from deterioration of the color image under high humidity.
  • the plasticized plastics for plastics and oils will not erase the colored image, and the surface strength (IGT big) of the upper color development sheet will be strong and excellent in printability. It is possible to obtain practically high quality products.
  • Acrylic latex which is the binder used in the present invention, has recently had a film temperature (MFT) of +45 or less, and performance parameters such as smoothness and binding force.
  • MFT film temperature
  • a methyl methacrylate and / or a steel as a hard monomer component and a ethyl methacrylate as a soft monomer component are used.
  • the acrylic latex used in the present invention generally has an irregular distribution in which each of the two types of monomer units has a small number of continuous irregularities.
  • Copolymers, alternating copolymers in which each unit is regularly and alternately arranged, and each unit obtained by a special copolymerization technique have been retained for a long time.
  • Has a multi-layered structure that has been developed and developed in recent years for example, a shell layer (shell) with a hard monomer, and a core (core) with a two-layer structure consisting of a fragile monomer).
  • the minimum temperature at which water evaporates and polymer molecules act on each other to form a film film is the minimum film formation temperature.
  • MFT using a thermal gradient tester with an acrylic lattice on a metal plate with a temperature gradient (for example, from 1 to +95).
  • the minimum temperature at which a dry film film is formed in an atmosphere excluding humidity after coating with a water dispersion (the temperature at which the film film becomes transparent and becomes the so-called minimum film formation temperature), and Obtain the whitening point temperature (temperature at which the film does not form and turns white).
  • the preferred amount of acrylic latex added is 100 parts by weight of inorganic developer in terms of solids by weight. 10 to 50 parts by weight. If it is less than 10 parts by weight, the smoothness cannot be improved, and if it is more than 50 parts by weight, the essential coloring ability is lowered, impairing the practical commercial value.
  • the present invention prepares a coating liquid containing an inorganic latex as a binder, a minimum film-forming temperature (FT) of +45, and the following acrylic latex, and -A major feature is that it coats the surface of the substrate with a coater and then dries it to give a color development sequence.
  • MFT minimum film-forming temperature
  • the normal drying condition At a temperature of 10 5 to ⁇ 50, which is dried 3 seconds after application, the continuous film film is difficult to form and the film becomes white as described above, and the binding strength is greatly reduced. I knew it would.
  • a latex for a binder that is widely known and used widely, there is a styrene butadiene-based latex, but according to the experiments conducted by the present inventors, the styrene and the latex are used.
  • the color density and the light fastness of the color image can be obtained depending on the ratio of the densities, the combined use of methyl methacrylate, or the modification of the force of the epoxy group and the change of the particle size, and the binding strength is sufficient.
  • the smoothness and dirt (smudge ') are insufficient.
  • the film film of acrylic latex is soft and further, the minimum film formation temperature (MFT) is set to +45 ° C or less.
  • MFT minimum film formation temperature
  • acrylic latex with a minimum film-forming temperature (MFT) of +45 or less was added to the inorganic dye, and it was not used as a coating liquid together with a dispersant, water retention agent, defoaming agent, etc. Apply it to a support such as paper using a coater method such as air knife, blade, roll, rubber dock, or curtain. Manufactures color-developing sheets for image recording materials.
  • MFT film-forming temperature
  • water-soluble binders such as starch, polyvinyl alcohol, carboxymethyl cellulose, dextran, etc., as desired, clay, calcium carbonate, magnesium carbonate, sachinho It is also possible to add pigments such as white pigment, titanium oxide, zinc oxide, urea resin pigment, plastic bigmen pigment, tark, aluminum, and aluminum hydroxide to the coating liquid.
  • the non-sulfur dyes that are particularly recommended for use in the present invention are the semi-synthetic solid acid compounds described in the above-mentioned JP-A Nos.
  • other non-color-developing agents are colorless ( ⁇ ⁇
  • the dye is adsorbed on the surface to develop color, which is used and the ratio per unit weight is used.
  • the larger the surface area the better the color development efficiency. That is, the smaller the particle size of the developer, the more advantageous.
  • the present invention makes the particle size of the inorganic developer as small as possible to improve the color development efficiency. However, it is most effective when trying to achieve smoothness improvement by preparing a fluid coating liquid that does not gel.
  • the particle size of the colorless developer is 5 to 6 micron.
  • a 5 to 6-micron mesh follow-up product was usually used, but according to the present invention, a 4-micron-cut product can be used. .5 It is a micro cutlet product and can be used to prepare coating solutions.
  • the present invention will be further described below with reference to Reference Examples and the most typical examples.
  • Reference Inversion The color-developing series used for the performance evaluation of the color-developing series obtained by carrying out the present invention [colorless (roico) dye-donative series, blue-developing] The manufacturing method of is described. All “parts” below represent parts by weight.
  • a colorless dye which is a colorless dye
  • 1 part of a black dye is used as a high-boiling solvent. It was dissolved in 100 parts of a dilute ruthenium-based organic solvent, and emulsified in acid-treated gelatin (isoelectric point 7.8) 1 0 parts of a 10-% aqueous solution of cesium. This emulsion was added to 150 parts of water in which 20 parts of Arabia gum were dissolved, and the pH of the solution was adjusted to pH 8.5 with caustic soda. The pH was kept at pH 4.4 with S acid for 10 hours, then cooled down to 21 and then added with 20 parts of 37% potassium aldehyde solution. , PH 10 with caustic soda, and a microphone mouth capsule. In the above-mentioned microcapsules of 100 parts (solid content), 1 part of 10 parts of polyvinyl chloride alcohol solution in water, 50 parts of wheat noodles
  • the minimum film formation temperature (MFT) + 20 is set to 50% of the total volume of the metallic membrane and the acrylic latex (the ratio of the total volume of the metallic membrane is approximately 30%).
  • Relay / 2-Ethyl relay Clear 1 5/4 5
  • the coating amount on the quality ⁇ of but substituting peripheral weight as coating solution in the same manner 4 0 / m 2 to 3 Te) is 4.8? / m 2 (solid content), applied with an air knife coater, dried and made into a developer series.
  • Test method The color development sequence obtained as described above was tested and measured by the following method.
  • the color development system was combined with the above color development system, and the color was developed through a force renderer, and the following values were measured with a color difference meter. The smaller the value, the higher the color density.
  • the strength when measured using an IGT tester is 5, 4,
  • Table 1 shows the characteristics of the color development system.
  • This M FT value is the value of the copolymer latex outside the present invention.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)

Abstract

Une feuille révélatrice de couleurs comportant un support pourvu d'une couche contenant un révélateur de couleurs récepteur d'électrons qui permet la formation de couleurs par un leuco-colorant donneur d'électrons, doit être utilisée en combinaison avec une feuille de formation de couleurs comprenant un support pourvu d'une couche de leuco-colorant donneur d'électrons, et contenant un révélateur de couleurs inorganique et un latex acrylique. Cette feuille permet d'éliminer les taches, d'améliorer l'égalité de surface et l'aptitude à l'impression.
PCT/JP1986/000135 1985-03-23 1986-03-20 Feuille revelatrice de couleurs pour materiaux d'enregistrement d'images WO1986005448A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60058948A JPS61217281A (ja) 1985-03-23 1985-03-23 画像記録材料用顕色シ−ト
JP60/58948 1985-03-23

Publications (1)

Publication Number Publication Date
WO1986005448A1 true WO1986005448A1 (fr) 1986-09-25

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Application Number Title Priority Date Filing Date
PCT/JP1986/000135 WO1986005448A1 (fr) 1985-03-23 1986-03-20 Feuille revelatrice de couleurs pour materiaux d'enregistrement d'images

Country Status (3)

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JP (1) JPS61217281A (fr)
AU (1) AU573972B2 (fr)
WO (1) WO1986005448A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5715996A (en) * 1980-07-03 1982-01-27 Mizusawa Ind Chem Ltd Novel clay mineral based color former for heat-sensitive copying paper and production thereof
JPS5816885A (ja) * 1981-07-23 1983-01-31 Mizusawa Ind Chem Ltd 新規な粘土鉱物系感圧複写紙用発色剤組成物及びこれを含有する水性塗液組成物
JPS5819474B2 (ja) * 1974-09-30 1983-04-18 富士写真フイルム株式会社 キロクシ−ト
JPS58153686A (ja) * 1982-03-09 1983-09-12 Mitsubishi Paper Mills Ltd ノ−カ−ボン複写紙用顕色シ−ト

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5819474B2 (ja) * 1974-09-30 1983-04-18 富士写真フイルム株式会社 キロクシ−ト
JPS5715996A (en) * 1980-07-03 1982-01-27 Mizusawa Ind Chem Ltd Novel clay mineral based color former for heat-sensitive copying paper and production thereof
JPS5816885A (ja) * 1981-07-23 1983-01-31 Mizusawa Ind Chem Ltd 新規な粘土鉱物系感圧複写紙用発色剤組成物及びこれを含有する水性塗液組成物
JPS58153686A (ja) * 1982-03-09 1983-09-12 Mitsubishi Paper Mills Ltd ノ−カ−ボン複写紙用顕色シ−ト

Also Published As

Publication number Publication date
AU5587786A (en) 1986-10-13
JPS61217281A (ja) 1986-09-26
AU573972B2 (en) 1988-06-23

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