WO1983002427A1 - Pressure-sensitive recording sheet - Google Patents

Pressure-sensitive recording sheet Download PDF

Info

Publication number
WO1983002427A1
WO1983002427A1 PCT/JP1983/000001 JP8300001W WO8302427A1 WO 1983002427 A1 WO1983002427 A1 WO 1983002427A1 JP 8300001 W JP8300001 W JP 8300001W WO 8302427 A1 WO8302427 A1 WO 8302427A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
color
pressure
sensitive recording
clay
Prior art date
Application number
PCT/JP1983/000001
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Ltd. Mitsubishi Paper Mills
Original Assignee
Tsukahara, Hirokazu
Torii, Takahiro
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 Tsukahara, Hirokazu, Torii, Takahiro filed Critical Tsukahara, Hirokazu
Publication of WO1983002427A1 publication Critical patent/WO1983002427A1/ja

Links

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
    • B41M5/1555—Inorganic mineral developers, e.g. clays

Definitions

  • the present invention relates to a pressure-sensitive recording sheet. More specifically, the present invention relates to an acid-treated clay, which is capable of almost completely removing aluminum-umion and has an aromatic adsorption index of 40 or more. After that, it is concerned with the improvement of color image storage of pressure-sensitive recording sheets that use a series of magnesium-based solid acids containing a substantial amount of magnesium ion as a color developer. It is a thing. Background technique
  • the pressure-sensitive recording sheet is generally composed of an electron-donating organic colorant (hereinafter referred to as a crystalline pigment), represented by a crystalline lactone, pentylcomethylene, or the like.
  • a color former an electron-donating organic colorant
  • a color former a montmorillonite-type clay mineral
  • activated clay which has been activated by acid treatment to increase its activity
  • a phenol compound a phenol compound
  • an aromatic compound based on the principle of developing a color by reaction with an electron-accepting color developer (hereinafter referred to as a color developer) such as a phosphoric acid or its metal salt. Lo cuff.
  • the top paper with cells coated on one side of the base paper, the above-mentioned mouth-opening case and the middle coat with the color developer coated on different sides of the same base paper, appropriately combined according to the purpose of use Copying can be obtained by applying pressure with a pen or typewriter.
  • active-white clay is most commonly used as a color developer.
  • This activated clay reacts well with the color former, and has the property of producing a deeper color, but the color developing ability has decreased over time?
  • the color image is discolored due to nitrogen oxides and the like when left naturally.
  • a reticulactone which is the most common coloring agent, develop a blue-violet color with the highest concentration between the activated clay and the activated clay, the acid of activated clay is used.
  • the strength is too strong. For this reason, there has been proposed a method of adjusting the fine clay side by adding an alkaline substance when adjusting the coating of active clay. However, over time, the effect is often lost due to the sulfuric acid band in the recrystallized base paper.
  • An object of the present invention is to provide an excellent pressure-sensitive recording sheet in which the above disadvantages are improved.
  • This object of the present invention has been attained by using a combination of a magnesium acetic acid and a hydroxybenzoic acid ester compound as a color developer.
  • the ferrite, mug, and nescia used in the present invention require a step of acid-treating a monmite-type night-type clay mineral.
  • the acid clay should have an A content of 5 to 30 parts by weight with respect to Si 100 parts by weight.
  • monmorillonite-type clay mineral is treated with sulfuric acid or hydrochloric acid, firstly, ion, Mg ion, and ion are eluted. Next, ion is eluted, and the iron / magnesia used in the present invention is one that has been subjected to treatment until the ion is substantially and completely removed.
  • the aromatic adsorption index of the treated clay at this time must exceed 40.
  • the aromatic adsorption index is an index that reflects the degree of adsorption capacity or activity of treated clay. Also, it is used as an index that indicates the degree of the specific surface area of the treated clay for convenience.
  • the aromatic adsorption index of 40 or more means that the activated clay used as a developer outside the present invention has an aromatic adsorption index of 2 C! ⁇ 40 ⁇ is very active]), which means that the specific surface area is very large, and furthermore, the crystal bioreactor This indicates that the number of acid sites in the weak acid portion contributing to the color development is increased. It also shows that the effect of the acid strength given by the sulfuric acid band in the base paper over time is unlikely to occur.
  • the aromatic adsorption index is determined by the following method.
  • the ground sample is dried at 150 ° G soil 5 deg. For 3 hours and allowed to cool to room temperature in a desiccator. This dried sample
  • the aromatic adsorption index can be increased by acid-treating this monolithic clay mineral.
  • the optimal acid strength to develop the highest concentration of crystallized retort lactones is not enough. It is considered to be promoted by light such as sunlight.
  • the acid point of the acid strength can be represented by the acidity of the treated clay, that is, the number of acid points having a certain acid strength.
  • serial magnetism used in the present invention is Fe
  • Si0 Mg + + is introduced into the 2 consisting processing clay nitrate mug roots ⁇ beam, mug chloride, roots ⁇ beam, perchlorate magnesiate U beam, formic acid magnesiate U beam, sulfate magnesiate U beam, hydroxide Use magnesium, magnesium carbonate, magnesium oxide, etc.
  • It may be introduced in an amount of 5 to 50 parts by weight, preferably 10 to 30 parts by weight.
  • Activated clay from which A ions have been removed is added to the solution in which the Mg salt is dissolved, and heat treatment is performed.
  • the Mg ion To fix the Mg ion, it is heated at 30 to 00 ° C. Subsequently, it is washed with water. At this time, a short-time treatment with a weak acid such as phosphoric acid may be performed.
  • a weak acid such as phosphoric acid
  • the silica-magnesia solid acid which is one of the developers used in the present invention, is a conventionally known activated clay, that is, a natural acid clay or an acid clay. Or those that have been subjected to only moderately acid treatment (naturally occurring metals such as magnesium, calcium, calcium, aluminum, iron, etc.) Thione is still abundant) and is a completely different kind of synthetic acid, so to speak, with a different concept from activated clay. That is, it is a synthetic silica-magnesia solid acid.
  • a hydroxybenzoic acid ester compound which improves the stability of a color image when used in combination with the magnesium oxide of the present invention is represented by the following general formula.
  • R represents A Le key group, ⁇ La Le key group, also device indicates ⁇ re Ichiru group, - C00R is - O Le DOO or C 0 la position relative 0H).
  • the amount of these hydroxybenzoic acid ester compounds added was 5 parts per 100 parts by weight of the silica / magnesia compound.
  • the addition method is as follows. It may be added as it is, but from the viewpoints of color development and surface smoothness, use a small amount of a dispersing agent to reduce the amount of polish, attritor, sand grinder, etc. It is preferable to add by pulverizing with a wet pulverizer.
  • hydroxybenzoic acid ester compounds used in the present invention particularly effective compounds are as follows.
  • Examples of the basic colorless dye as the color-forming agent of the present invention include crystal phenol, phenol phenol, phenol phenol and phenol phenol.
  • kaolin, clay, and tar are further used as bulking agents.
  • Styrene as a binder to be applied to the base paper
  • -Latex-based binders such as phenolic-based latex and acrylic-based latex, oxidized starch, ethereal starch , Carboxymethylcellulose, hydroxyethyl phenolic cellulose, methylphenol phenolic cellulose, polyvinyl phenolic cellulose, case Water-soluble polymer binders such as iron, gelatin, soybean tannin, alginic acid, etc. can be used alone or in combination.
  • One addition amount is 10 to 40 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of magnesium magnesia and hydroxybenzoic acid ester conjugate. 30 parts by weight.
  • the color former is dissolved in a solvent to form a micro cuff. Cellify and apply to base paper.
  • a solvent natural or synthetic oil alone or hail_
  • _ CMFI Can be used in combination with one.
  • solvents are cottonseed oil, kerosene, and c.
  • the microcapsule containing the color former is applied to a sheet such as paper along with various additives, plying agents, antioxidants, antifouling agents and surfactants. .
  • the pressure-sensitive recording sheet according to the present invention has such effects that the color developing ability does not decrease over time and that it has excellent resistance to discoloration and fading due to nitrogen oxides and light.
  • Li ⁇ Na wells clay minerals (1 1 0 ° C dry matter in weight percent as a reference, ignition loss 5.8, Si0 2 7 8 ⁇ 0 , A £ 2 s 1 3 ⁇ 0 , Fe 2 0 3 1 • 9, CaO 0.9, MgO 2.)) are treated with sulfuric acid to obtain ⁇ , Fe, Ca,- 1 t
  • Hydroxylene seno-leose 5 parts water '145' was crushed with wool mill for 2 days.
  • coloring paper there are commercially available products that include crystal pie, lettactone, and pen ⁇ -yllomethylethylene blue as the main component of the coloring agent.
  • Mitsubishi NCR paper N-40 paper blue was used. Table 1 shows these colors.
  • silica / magnesia is used as a developing agent (that is, only a hydroxybenzoic acid ester compound is used from the developing paper of the above example).
  • a comparative example an alternative to the hydroxybenzoic acid ester compound of the color developing paper of the above example was used as a comparative example.
  • Table 2 shows the degree of yellowing caused by exposure to NOx gas or sunlight on white paper.
  • the developed paper of the present invention exhibits the same yellowing durability as that of the blank, whereas the comparative example (combined use of magnesia and Pisphenol A) is significantly yellowing.] Thus, the inventive step of the present invention is recognized.
  • Table 5 shows the NOx fastness of the colored part.
  • the NOx fastness of a color image is remarkably improved.
  • Table 4 shows color development with a medium intensity calendar.
  • the one-shot rendering color is the value measured by a Macbeth densitometer (reflection density) when color is developed with a pressure of 501 1cm by combining color-developed paper and colored paper.
  • a Macbeth densitometer reflection density
  • ppm concentration
  • the color biomarker (CB) is the one that uses the crystal bioreactone alone.
  • the micro cuff is dissolved in a solvent. ), The stability of the color image (sunlight,

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
PCT/JP1983/000001 1982-01-09 1983-01-07 Pressure-sensitive recording sheet WO1983002427A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP57/2175820109 1982-01-09
JP57002175A JPS58119890A (ja) 1982-01-09 1982-01-09 感圧記録シ−ト

Publications (1)

Publication Number Publication Date
WO1983002427A1 true WO1983002427A1 (en) 1983-07-21

Family

ID=11522023

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1983/000001 WO1983002427A1 (en) 1982-01-09 1983-01-07 Pressure-sensitive recording sheet

Country Status (2)

Country Link
JP (1) JPS58119890A (enrdf_load_stackoverflow)
WO (1) WO1983002427A1 (enrdf_load_stackoverflow)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60198290A (ja) * 1984-03-22 1985-10-07 Fuji Photo Film Co Ltd 記録材料

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5016969B2 (enrdf_load_stackoverflow) * 1971-09-03 1975-06-17
JPS5139566B2 (enrdf_load_stackoverflow) * 1973-01-12 1976-10-28
JPS5597982A (en) * 1979-01-19 1980-07-25 Fuji Photo Film Co Ltd High solid content active clay slurry composition and production thereof
JPS55103994A (en) * 1979-02-01 1980-08-08 Mizusawa Ind Chem Ltd Color-developing agent composition for pressure-sensitive transfer paper, its preparation and impression paper for pressure-sensitive transfer

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5489816A (en) * 1977-12-27 1979-07-17 Fuji Photo Film Co Ltd Color developing ink

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5016969B2 (enrdf_load_stackoverflow) * 1971-09-03 1975-06-17
JPS5139566B2 (enrdf_load_stackoverflow) * 1973-01-12 1976-10-28
JPS5597982A (en) * 1979-01-19 1980-07-25 Fuji Photo Film Co Ltd High solid content active clay slurry composition and production thereof
JPS55103994A (en) * 1979-02-01 1980-08-08 Mizusawa Ind Chem Ltd Color-developing agent composition for pressure-sensitive transfer paper, its preparation and impression paper for pressure-sensitive transfer

Also Published As

Publication number Publication date
JPS58119890A (ja) 1983-07-16
JPH0326150B2 (enrdf_load_stackoverflow) 1991-04-09

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