FR2539751A1 - MAGNETIC AQUEOUS INK FOR THE INKJET RECORDING METHOD AND INKJET RECORDING METHOD USING THE AQUEOUS INK - Google Patents

Abstract

THE INVENTION RELATES TO A WATER-BASED MAGENTA INK AND TO AN INKJET RECORDING PROCESS USING THIS INK. THE AQUEOUS INK ACCORDING TO THE INVENTION CONTAINS (A) AT LEAST ONE WATER SOLUBLE COLORANT OF GENERAL FORMULA (CF DESIGN IN BOPI) IN WHICH R REPRESENTS HYDROGEN OR AN ALKYL GROUP, R AND R REPRESENT EACH (CF DESIGN) IN BOPI) OR R REPRESENTS AN ALKYL GROUP OR AN AMINO GROUP, M IS EQUAL TO 0, 1, 2 OR 3 AND N IS EQUAL TO 0, 1 OR 2, R REPRESENTS AN ALKYL GROUP OR A HALOGEN, P IS EQUAL TO 0 , 1 OR 2, R REPRESENTS SO OR COO, R REPRESENTS HYDROGEN, -SOM OR A HALOGEN, Q IS EQUAL TO 0, 1 OR 2 AND M REPRESENTS A METAL ALKALINE CATION, AN AMINE CATION OR AN AMMONIUM ION , (B) WATER AND (C) A HUMECTANT.

Description

2539751.

  The present invention relates to an aqueous ink

  improved for ink jet recording and a process for

  ink jet recording using said aqueous ink.

  Recently, there has been a great deal of research and development in the field of ink-jet recording technology to improve the reproduction of color images. In particular, various studies have been made to develop inks. able to reproduce the three

  primary colors, that is, cyan, magenta, and current yellow.

  However, an ink capable of providing satisfactory magenta color images, having high water resistance and light resistance and suitable for use in ink jet recording by the ink jet has not been obtained. for example, the inks containing Acid Red C 52 or Acid Red CI 227, both of which are known conventional magenta dyes, have the disadvantage that the images obtained by these inks have a poor color tone.

  and do not have sufficient light resistance for use

  In addition, the inks containing Acid Red CI 92 or Acid Red CI 94, both also conventional magenta dyes, have the disadvantage that the resulting images have poor resistance to light and water. are suitable

  therefore not for practical use.

  In addition, since a magenta ink capable of giving a perfect magenta color has not been obtained, when producing a magenta color, it is necessary to choose from among a certain number of magenta inks an ink capable of giving a uniform color. color that

  looks the most like the ideal magenta.

  On occasion, it is necessary to appeal to

  some special means of color correction to reproduce

  magenta images with a good balance of color tone.

  Generally, among the yellow dyes, the magenta dyes and the cyan dyes, the magenta dyes have particular reflection spectra and the images obtained with the magenta dyes considerably fade or disappear completely on exposure to light, thus causing a sharp decrease in image density and an incorrect color balance in the

colorful images.

2539751 X

  For the production of an ideal magenta color by a magenta dye, it is necessary for the dye to reflect light sufficiently in two separate spectral bands of reflection, i.e. in a 400-500 nm spectral band and a spectral band of 600-700 nm, with a good balance of the light reflection in both spectral bands However, it is extremely difficult that the magenta dyes generally used fulfill this requirement because of their chemical structures The imbalance of the reflection of light in both

  spectral bands makes the images produced reddish or bluish.

  In addition, since dyes capable of producing a color of a tone very similar to magenta contain strained chemical bonds in their molecule, they are vulnerable to external effects such as exposure to light and their structure is likely to be modified. or decomposed by these effects; As a result, the images formed by the magenta dyes fade

  more easily compared to the images formed by other

  rants. To overcome the disadvantages of conventional magenta inks, especially for use in recording

  inkjet, various proposals have been made, such as

  However, a magenta ink which is sufficiently suitable has not yet been proposed for color correction, particular choices of the components in the ink compositions and the use of a particular recording medium in combination therewith.

  for practical use in ink jet recording.

  It is necessary that any ink for

  the use in inkjet printing satisfies the conditions of

  following statements to give an excellent impression.

  First, for the ink to be compatible with ink droplet formation and the directional adjustment of ejected ink droplet currents, its viscosity, surface tension, specific electrical conductivity, and density are required. are each in certain ranges

appropriate.

  Secondly, it is necessary that precipitates do not separate from the ink, as a result of coagulation, precipitation, chemical modification of slightly soluble components or other causes, for a long period of continuous use or over time. storage, or during periods when the equipment is not in use The physical properties of the ink must not be changed otherwise during the periods mentioned above If the separated solid components or the viscous materials in the ink are fixed around the nozzles, or if the

  physical properties of the ink vary, deviating from

  predetermined physical properties obtained at the time of preparation

  the desired quality of printing, the desired stability of ejection

  the ink and the desired ink ejection response

  can not be obtained since the ejection of the ink is gener-

  typically made from nozzles with a diameter of about 10 to 10 μm. Thirdly, it is desired that the ink give the printed image a high contrast and sharpness appropriate in a conventional ink, the contrast and sharpness of the printed images

  are increased by increasing the content of a dye in the ink.

  However, as the dye content in the ink increases, clogging of the nozzles occurs more easily. Thus, a dye which is highly soluble in the ink solvent and which has a high extinction coefficient is desired. , we do not have

still got such a dye.

  Fourth, it is necessary that printed images

  ink dries quickly In a conventional ink, a quantity of

  relatively large amount of a humectant is contained in the ink -

  to avoid clogging of nozzles with dried ink during periods when the recording apparatus is not in use Due to the use of this large amount of humectant, rapid drying of printed images a special paper

  able to absorb strongly and quickly the ink However, the use of

  This special paper will spread the images

  printed matter and, of course, other papers such as ordinary paper

  can not be used for the ink.

  Fifth, it is necessary for the ink jet recording ink to be such that the printed images are resistant to water, light, and physical wear and tear.

are clear.

  So far, there have been many proposals for a magenta ink for inkjet printing, but from a practical use point of view, no satisfactory ink has been found that is capable of to fulfill the conditions described above. The present invention therefore aims to propose

  an aqueous ink for ink-jet recording, which satisfies

  Completely the conditions described above. In other words, the object of the present invention is to provide an aqueous magenta ink for inkjet printing which does not lead to

  the closing of the nozzles, a variation of quality or a separation

  precipitation during storage, but which exhibits excellent ink ejection stability and good ink ejection response, exhibits at most small variations in physical properties when uses

  for a long time without continuous recycling or in

  intermittently and which gives printed images

  not having and having resistance to water and superior light,

  high fineness and high image density.

  Another object of the invention is to propose a

  ink jet recording process using the aqueous ink

  above, which allows a perfect reproduction of the magenta in the image formation, these magenta images having a high resistance

with water and light.

  The first object of the invention is achieved by means of an aqueous magenta ink comprising at least one of the water-soluble dyes represented by the following formula, water and a humectant, if necessary with addition of other additives R, R 1

R 3 / O_N + R 2

  In which R is hydrogen or an alkyl group, R and R each represent -A + R (503 M) or (SO N) n R 7) (R) mo R 7 represents an alkyl group or an amino group, m is 0O 1, 2 or 3 and N is 0, 1 or 2, R is alkyl or halogen, p is 0, 1 or 2, R 5 is 503 or COO , R 6 represents hydrogen, -SO M + or a halogen, q is 0, 1 or 2 and M represents a

  alkali metal cation, an amine cation or an ammonium ion.

  The second object of the invention is achieved with an ink jet recording method in which images are recorded by using the aforementioned aqueous ink on a recording medium containing at least one component. selected from water-soluble metal salts of which the metal is di or polyvalent, alkylamine salts, quaternary ammonium salts, compounds having two or more amino groups, compounds having two or more amido groups

  and basic polymer products -

  Representative examples of hydrophilic dyes

  lolubles of the above formula to be used according to the invention are

  listed in the following Table 1.

253 '975 1 li

TABLE 1

CH'l (1) (2) EC, Cli 3

+ HN O

Mo; S- (its M'l CE 3 so,

NH 2 NN 2

  q'd-, S O -, + ne - (OY SO IN Ji N c H O; (3) (4) CRI TABLE 1 (cont'd 1) +

0 NE

C m r '

+ CE

0 NE

That,> 3 m (6) 0; 503 Na

CH 3 CE 3

EN O + E

  -MOA (7) Hj C C 3 503 Na c 4 H 9 + c 4 H 9

IN O

C 4 H_

  Mtl S 503 M 9c H 9c 4m + c 4 Hg RN oc

im ±

TABLE 1 (continued 2) -

CES CES

N O N + +

c 503 M (10) H 3 c SOI Cli

+% NE +

mo 35 O 503 M (11)

CE 3 +

HN O N +

  É 07 S sosm (12) c H 3 CH 3 c Ea O; L sosm (13) c H 3 fold 3 + CES

HN O ONH

  my S sd, 3m + (14) Es H 3 c Ct 07 cz

25397511,

  TA Bf LEAU 1 (continued 3) CH, SO Sm Mbs O ONE + CE O co CE, month (D-5) (16)

(17>

  In formulas (1) to <17) above, 14 may be, for example, -Na, Li * + + H Li, K, -Iq (CH 2 CH 2 OH) 3, -M (o H 3 ) 3 ', - & (a C 2 H 5) 3 or -N 414 * MC may be the same or different in

the molecule of each dye.

  2539751 li TABLE 1 (cont'd 4) Case (S Og Li) 2 (18) CES I S Os Itla Nao 2 O r NII Si C):

Na O 3 & ,: bow i-

(19) -

NEI N-H 2

EN O +

Na O 3 S-4 NE 2 Os Na Na O 3 ms

CE 3 + CH,

EN-O-O-3 C; 03 Li

Lioa O 3-

S- (20) (21) cul + c 4 H 9

IN N

  ## STR2 ## ## STR1 ##

+ CE 3

KO NE

c SOSK (23) So

C 11-1 CSE 7

  Na Oa SNC 3 Soa Na (24) 9 NaCl 3 CH 3 (LiO 5) 503 Li C 2 SO 4 Na (26) c 2 HS o -SO 3 Na The properties of aqueous magenta dyes for use in The invention is as follows: (1) The color error of the dyes is 450 or less and their

  shade is 35 or less, expressed in values of

  These values indicate that the dyes for use according to the invention have a color tone which is extremely close to the color tone.

of an ideal magenta.

  (2) The dyes are highly soluble in (i) the polyalcohols and their alkyl ethers which are used as components of the humectants in the aqueous inks according to the invention and in (ii) the water which is one of the The main components of the aqueous inks according to the invention As a result of this high solubility in the polyalcohols, in their alkyl ethers and in water, a high reliability of the ejection of

ink droplets.

  The maximum solubility of dyes in pure water is 18%

  by weight or more and their maximum solubility in diethylene

  glycol is 15% by weight or more.

  (3) Although the dyes to be used in the invention are xanthene dyes, the images formed by the dyes are

  strongly resistant to light For example, their attenuation rate

  is 5% or less when exposed for 6 hours

  in the light of a charcoal arc lamp.

  When printing is done with the dyes on one -

  recording medium containing at least one selected component

  among the water-soluble metal salts whose metals are di-

  or polyvalent alkylamine salts, quaternary ammonium salts, compounds having two or more amino groups, compounds having two or more amido groups and basic polymeric products, the water resistance of the printed images is all particularly high For example, when the images are immersed in water at 300 C for 1 min, their attenuation rate

is 3% or less.

  An aqueous ink according to the invention consists of a dye of the above formula, water and a humectant. If necessary, a water-soluble preservative and an anti-mold agent may also be added to the ink. , an increasing agent

  solubility to increase the solubility of the dye in the soil.

  of ink, a pH adjusting agent, a control agent of

viscosity and other additives.

  As humectants for use in the aqueous ink according to the invention, the polyalcohols and their ethers can be used

  It is preferable that the amount of humectant is

  taken in the range of 5 to 30% of the weight of the ink.

  Examples of the polyalcohols are the following: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,

  glycerol, polyethylene glycol and polypropylene glycol.

  Examples of polyalcohol alkyl ethers are

  the following ones: monoethyl ether of ethylene glycol, mono-

  Ethylene glycol butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether. Glycerol and diethylene glycol constitute a specially effective humectant for use in the recording process. According to the invention a particularly useful mixture is a glycerol / diethylene glycol mixture in a ratio of 1/1 to 1/5, with which the initial properties of the ink can be maintained even during a long period of continuous use or storage, or during the periods in which the appliance is not in use; thus obtaining a stability of the ink droplets and a reliable ejection response of ink droplets,

  especially after a prolonged period without the use of

mera.

  It can be added to the mixture of glycerol and diethylene-

  glycol one or more of the other humectants mentioned above.

  In this case, it is preferable that the maximum amount of the humectant

  added either 40% by weight of the mixture of 4 rol gly and diethylene-

  glycol. Examples of water-soluble preservative and anti-mold agents which can be used are the following chemicals: 2,2-dimethyl-6-acetoxy-1,3-dioxane, 2539,751-dihydroacetate,

  sodium, p-hydroxybenzoated butyl, potassium sorbate, 1-oxo

  sodium pyridine-2-thiolate, anionic surfactants, "Deltop 33" (sold by Takeda Chemicai Industries Ltd.), and "Hokucide LX-2" (manufactured by Y. Hokko Chemical Industry Co., Ltd.). In the present invention, water is used as the main component of the solvent and the following solubility increasing agents can be mixed with water to increase the solubility of the dyes in the ink solvent: amine derivatives, such as triethanolamine; nitrogenous heterocyclic compounds, such

  N-methyl-2-pyrrolidone, 2-pyrrolidone and 1,3-dimethylimidazoline

  dinone; intramolecular esters of hydroxycarboxylic acids such as valerolactone and caprolactone; and ethylene glycol acetates,

  such as ethylene glycol monomethyl ether acetate.

  In the present invention, it is possible to use

  Viscosity control agents are any of the known chemicals as long as they do not have adverse effects on the solvents and dyes used.

  these chemicals are polyvinyl alcohol, hydroxyethyl

  cellulose, carboxymethylcellulose, methylcellulose, water-soluble acrylic resins, gum arabic, dextrin,

  casein, pectin, gum tragacanth and polyvinylpyrrolidone.

  According to the invention, any of the products can be used optionally as p-adjusting agents as long as they do not have a deleterious effect on the ink and they can

  set the p H of the ink in the range of 9.0 to 11.0.

  Examples of such pH adjusting agents are amines, such as diethanolamine and triethanolamine; alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide; and alkali metal carbonates, such as lithium carbonate, carbonate of

sodium and potassium carbonate.

  Other products that can be used as additives are as follows: To maintain the specific electrical conductivity of the ink above 1 m cm (25 C), ink agents are used above 1 mf -1 cm (at 250 ° C.), agents are used.

2539751 J,

  Specific Electrical Conductivity Control Examples of these electrical conductivity control agents are the

  inorganic salts, such as potassium chloride, ammonium chloride,

  monium, sodium sulfate and sodium carbonate and water-soluble amines, such as triethanolamine. As chelating agents, the following products can be used, for example: ethylenediaminetetraacetate

  sodium, trisodium nitrilotriacetate, hydroxyethylethylenediamine

  trisodium triacetate, sodium diethylenetriaminepentaacetate

and disodium uramilacetate.

  Examples of anti-rust agents for the nozzles are: acid sulphites,

  sodium thiosulfate, ammonium thioglycolate, diisopropyl nitrite

  propylammonium, pentaerythritol tetranitrate and nitrite

dicyclohexylammonium.

  Other additives, for example hydro-

  soluble ultraviolet absorbers, water-soluble

  Infrared and magnetic fluids in which ultrafine magnetite particles and latex emulsions are dispersed may be used, if deemed necessary, in particular embodiments of an aqueous ink for

  the ink jet recording according to the invention or for the use

  in a particular device.

  The following examples illustrate the invention without

however, limit its scope.

EXAMPLE 1

  A mixture of the following components is heated to 70 ° C. and stirred until they are completely dissolved. The mixture is adjusted to pH 10.0 by the addition of NaOH. The mixture is then filtered twice through a membrane. filter having a mesh size of 0.2 μm; an aqueous ink N O 1 is thus prepared for

  the ink jet recording according to the invention.

  % by weight Color (1) of Table 1 (M = Na) 3.0 Diethylene glycol 22.5 Glycerol 7.5

2539751 ,.

  by weight "Deltop 33" (Takeda Chemical Industries, Ltd) 0.2 Ion-exchange-treated water 66.8 The ink is then subjected to the following tests (1) Image-sharpness and Dry-down test the image. The ink is sprayed through a nozzle of 30 μm inner diameter with pulses of 100 kHz frequency which break the ink stream into isolated droplets, which then strike a high quality sheet of commercial paper. , a commercial ink-jet recording sheet from Jujo Paper Mfg Co., Ltd. and a commercial ink-jet recording sheet from Mitsubishi Paper Mills, Ltd. This produces clear images on each of the sheets. The time required for the drying of the printed image is not greater than 10 S at normal ambient temperature and humidity.

(2) Conservation test.

  Samples of the ink are sealed in glass containers and subjected to the following storage tests at -200 C for 1 month; b storage at 40 C for 1 month; c storage at 20 C for 1 year; and

  storage at 900 C for one week.

  It is absolutely not observed in the separation storage of precipitates in the ink In addition, no variations are detected

  properties or color of the ink.

  (3) Stability test of ink droplet ejection.

  Ink jet printing is performed as in the image sharpness and image drying test described above continuously for 1000 h. There is no sign of clogging of the image. nozzle or variation of the direction of ejection of the droplets

  ink; on the contrary, a stable record is maintained.

  (4) Droplet ejection response test.

  After inkjet printing as described in (1), the apparatus and the ink are allowed to stand at ambient temperature and humidity for one month, after which they are used again to perform the ink-jet recording in the masts

  conditions described previously in (1) As in (3) above

  above, there is no variation in ejection stability

ink droplets.

  The above test is repeated in the same manner, except that the apparatus and the ink are allowed to stand at 40 ° C. and 30% relative humidity for 1 week, instead of the ambient temperature and humidity. For a month again, there is no change in the stability of ejection of ink cartridges.

  (5) Light resistance of recorded images.

  The recorded images are exposed to the light of a charcoal arc lamp for 6 hours. The attenuation rate of the images

is not more than 5%.

EXAMPLE 2

  Example 1 is repeated except that the components of the ink used in Example 1 are replaced by the components

  following; an aqueous ink n 2 is thus prepared for recording

  with the ink jet according to the invention.

  Color (2) of Table 1 (M = Li) Diethylene Glycerol "Hokucide LX-2" (from Hokko Chemical Industry Co., Ltd) Ion-exchange-treated water% by weight 2.5 22.5 7.5 0.2 67.3

EXAMPLE 3

  The example is repeated except that the components

  of the ink used in Example 1 by the following components; an aqueous ink n 3 is thus prepared for recording at

ink jet according to the invention.

Colorant (3) of Table 1 (M = Li)

Diethylene glycol -

  Glycerol "Deltop 33" (from Takeda Chemical Industries, Ltd) Ion-exchange treated water% by weight 3.0 22.5 7.5 0.2 66.8

EXAMPLE 4

  Example 1 is repeated except that the components of the ink used in Example 1 are replaced by the components

  following; an aqueous ink 4 is thus prepared for recording

  with the ink jet according to the invention. Color (6) of Table 1 (M = Na) Diethylene Glycerol "Hokucide LX-2" (from Hokko Chemical Industry Co., Ltd) Ion-exchange-treated water% by weight 3.0 22.5 7.5 0.2 66.8

EXAMPLE 5

  Example 1 is repeated except that the components of the ink used in Example 1 are replaced by the components

  following; an aqueous ink N O 5 is thus prepared for recording

  tremenc inkjet according to the invention.

  Color (9) of Table 1 (M = Li) Diethylene glycol Glycerol "Deltop 33" (from Takeda Chemical Industries, Ltd) Ion-exchange-treated water% by weight 2.5 22.5 7.5 0.2 67.3

COMPARATIVE EXAMPLE 1

  Example 1 is repeated except that the components of the ink used in Example 1 are replaced by the following components;

  a comparative aqueous ink No. 1 is thus prepared for recording

very ink-jet: -

  Red Acid C I 92 Diethylene Glycol "Deltop 33" (from Takeda Chemical Industries, Ltd) Ion-exchange-treated water% by weight 3.0, 22.5 7.5 0.2 66.8

2539751 ,,

COMPARATIVE EXAMPLE 2

  Example 1 is repeated except that the components

* sants of the ink used in Example 1 by the following components;

  a comparative aqueous ink n 2 is thus prepared for recording

  Ink jet: Acid red CI 52 Diethylene glycol Glycerol "Deltop 33" (from Takeda Chemical Industries, Ltd) Ion-exchange water% by weight 2.5 22.5 7.5 0.2 67 3

COMPARATIVE EXAMPLE 3

  Example 1 is repeated except that the components

  of the ink used in Example 1 by the following components;

  a comparative aqueous ink n 3 is thus prepared for recording

  Inkjet: Direct Red CI 9 Diethylene Glycerol "Deltop 33" (from Takeda Chemical Industries, Ltd) Ion-exchange water% by weight 2.5 22.5 7.5 0.2 67 3 The same tests as in Example 1 are followed by the inks

  No. 2 to 5 according to the invention and the aqueous inks

  1 to 3 The results obtained are shown in the table below. 2539751 i

TABLE 2

  Aqueous inks No. 2 to 5, such as the aqueous ink N O 1 of Example 1, in image sharpness and image drying, are excellent in all matters relating to

conservation, stability

  droplet ejection unit and the ejection response of the droplets

  ink cartridges and the light resistance of the recorded images.

enre.

  On the contrary, the comparative ink N O 1 has a bad

  conservation and poor ejection response of the droplets with regard to the light resistance of the images

  recorded, this ink is far from suitable for practical use.

  The comparative aqueous ink No. 2 has poor preservation.

  With regard to the light resistance of the recorded images, this comparative ink is the same as comparative aqueous ink # 1 and can not be used in practice.

  Comparative aqueous ink N O 3 has poor ink drop ejection stability, poor ink drop ejection response and poor light resistance of the recorded images and is also unsuitable

to practical use.

  Examples Example Example Comparative Comparative Comparative Example

2 to 5 1 2 3

  Picture sharpness and drying Good Good Good Good Good Good Bad Bad Good

Stability of ejection

  ink drop Good Good Good Good Ink drop ejection Good Good Bad Good Bad Light fast Good Good Good Good Good 2539751 j, In an inkjet recording process according to the according to the invention, images are recorded using the aqueous ink described above on a recording medium which contains at least one treatment agent selected from water-soluble salts S of di or polyvalent metals, alkylamine salts, salts and the like. quaternary ammonium compounds, the compounds having two or more amino groups, the compounds having two or more amido groups

  and basic polymeric products.

  The recording medium to be used in this program

  The present invention provides, for example, the following two methods: In a process, a support material is formed on a support material

  a layer containing at least one of the treatment agents

  mentioned above. In the other process, a material of

  support in a solution containing at least one of the treatment agents

  above, so that the support material is impregnated with the treatment agent, without formation on said support of the first-mentioned layer. In one way or another, a better result is achieved in the first method when using a somewhat larger amount of the treating agent

than in this last process.

  When preparing the recording medium in-use

  If it is a water soluble salt of di or polyvalent metal, it is preferably

  to use the metal salt in an amount of 0.2 g / m 2 or more,

  in particular 1.0 g / m 2 or more.

  Specific examples of these metal salts

water-soluble are as follows.

  Examples of divalent metal salts: Mg C 12, Ca Br 2, Ca C 12, Ca (N OO) 2, Ca I 2, Zn C 12, Zn Br 2, Zn I 2, Zn (C 103) 2, Zn 504, Zn (N 03) 2, Sr I 2, Sr Br 2, Sr C 12, Sr (NO 3) 2, Ba C 12, Ba (N O 3) 2, Ba (OH) 2, Ba I 2, Ba Br 2, Fe (N OO) 2, Ni (N OO) 2,

Ni 504, Ni C 12, Cu C 12, Cu SO 4.

  Examples of trivalent metal salts: Al C 13, A 12 (504) 3, Al (N O 3) 3, Sc C 13, Sc (N O 3) 3, Sc 2 (504) 3,

  Ga (N 03) 3, Ga C 13, Ga 2 (504) 3, In C 13, Fe (N O 3) 3 and the alums.

  Examples of tetravalent metal salts:

  Ti C 14, Ge C 14, Zr (504) 2, Sn C 14, Sn (504) 2, Pb (CH 3 CO O) 4 -

253975 1,

  Of these water-soluble metal salts,

  in particular use in the recording medium of the invention

  A 13 C 13, A 12 (504) 3, Al (N O) 2, Zn C 12, Zn 504, Sn C 4, Ca C 12, Mg C 12

and In C 13.

  When preparing the recording medium using an alkylamine salt, it is preferable to use the alkylamine salt in an amount of 0.05 g / m 2 or more, particularly in

amount of 0.2 g / m 2 or more.

  Specific examples of these alkylamine salts are the following: decylammonium acetate, undecylammonium acetate,

  dodecylammonium, tridecylammonium acetate, tetradecyl acetate

  ammonium, pentadecylammonium acetate, hexadecylammonium acetate, heptadecylammonium acetate, octadecylammonium acetate, acetate

  of nonadecylammonium, eicosylammonium acetate, decyl chloride

  ammonium, undecylammonium chloride, dodecylammonium chloride, tridecylammonium chloride, tetradecylammonium chloride, pentadecylammonium chloride, hexadecylammonium chloride, heptadecylammonium chloride, octadecylammonium chloride, chloride

  of nonadecylammonium and eicosylammonium chloride.

  When preparing the recording medium for use

  reading a quaternary ammonium salt, it is best to use

  the quaternary ammonium salt in an amount of 0.1 to g / m 2 or more.

  Specific examples of these quaternary ammonium salts are: lauryltrimethylammonium bromide, lauryltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and

  hexadecyltrimethylammonium chloride.

  When preparing the recording medium for use

  reading a compound having two or more amino groups or a compound having two or more amido groups, it is preferable to use

2539751 "

  the compound in an amount of 0.05 g / m or more, in particular in

quantity of 01 g / m 2 or more.

  Specific examples of compounds having two or more amino groups and compounds having two or more amido groups are as follows:

  (1) Condensation products of o or p-toluidine and formaldehyde

  dehyde, for example (2) Menthol derivatives, for example CH 3 H 3 C CH

  (3) Products prepared by the addition of epichlorohydrin to ethylene

diamine.

  (4) Derivatives of aminobenzoates, for example -

CH C ^ H

3 2 5

H C 00 CH CCHN

2 N 02, 2 -, CH

CH 25

  (5) Other compounds having two amino groups, for example

2539751 ,.

amanozine, NH

HOCHCH 3

0 C H 2 HC 00

NH 2

NH 2

p-aminorephedrine, kynurenine

  When preparing the recording medium for use

  reading a basic polymer product, it is best to use the

  basic polymer product in an amount of 0.05 g / m 2 or more, in particular

  in an amount of 0.1 g / m 2 or more.

  Specific examples of these basic polymeric products are (1) polyvinyl compounds having the following quaternary ammonium group units:

R R

1 13

C n_ tc 7 T i

R R 4-N-R 6 X

2 4 6

R 5 X

R R

R It t R, 1,3 or C _ C

T T

R 2 y l +

R -N -R X

4, 6

  In which R 1 to R 6 are each hydrogen or halogen, alkyl, phenyl, hydroxyl or alkoxy, Y is an ether group, an ester group, an alkylene group, a -CH 2 CH 2 group or a phenyl group and N is an integer of 10 to 1000, and

  (2) natural proteins such as gelatin and albumin.

R 4 R 4

N NH

  When preparing the recording medium by impregnating a support with one of the above-mentioned treating agents, the plain paper, the unbonded paper or a water-absorbing plastic film may be used as the support material, and impregnates the support material with the treating agent by dipping the support material into a solution or dispersion of the treating agent or by applying the solution or dispersion onto the support material. plain paper with a gluing degree of 20 seconds or less, whiteness of 75% or more, uniformity of 10 to 150 and air permeability of 3 S to 120 S and the paper is impregnated

  with one of the treatment agents by the method mentioned above.

  above. When preparing the recording medium by forming a layer containing at least one of the treatment agents mentioned above, a support material consisting essentially of cellulose, a synthetic paper, a plastic film, is used as the support material. , a glass plate, a metal plate

  metal sheet, regardless of the absorption properties

  the ink of the support material.

  In the above layer, in addition to the treatment agents, a binding agent and other additives may be added if necessary.

such as a pigment.

  Binders which can be used for this purpose can be roughly classified into two groups, resin-type binders and latex-type binders. Examples of these agents are as follows: Oxidized starch resin binders, etherified starch, starch esterified, dextrin, casein, gelatin, gum arabic, vegetable protein, cellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, resin

  of maleic anhydride, polyvinyl acetate, polyvinyl butyral, poly-

  acrylamide, combinations of the above polymers, copolymers of the above polymers and modified polymers derived from the above polymers.

2539751,

  B Binders of the latex type of polyvinyl acetate latex, styrene-isoprene copolymer latex, styrene-butadiene copolymer latex, acrylic polymer latex, acrylic-vinyl acetate copolymer latex, methyl methacrylate-butadiene copolymer latex and

  combinations and modifications of the latexes above.

  Examples of the pigments to be used in the layer are the following: clay, talc, diatomaceous earth, calcium carbonate, calcium sulphate, magnesium carbonate, magnesium sulphate, barium sulphate, titanium oxide, zinc oxide, zinc sulphide, zinc carbonate, titanium white, aluminum silicate, silicon oxide, calcium silicate, aluminum oxide, aluminum hydroxide, zeolite. Among the pigments mentioned above, it is preferred to use in the layer calcium carbonate,

  magnesium, barium sulfate and titanium white.

  This layer containing the treatment agent can be prepared by various techniques. For example, in a process, a binder layer and the additives are formed on a support material and then applied to the layer.

  previously mentioned treatment agents In another

  given, a solution or

  persion of a binder, additives and a treatment agent and

  then dry the applied layer.

  More particularly, in the first method

  In a preferred embodiment, a dispersion consisting essentially of a binder and the additives is applied to a carrier material by a doctor blade coating, air knife coating, roll coating, bar coating and wire, spray coating, etching coating or enductlon coating

  rolls and the dispersion applied by the application is

  cation of hot air or heat, with a coating de 8 t ranging from 0.1 to 60 g / m, preferably between 3 and 20 g / m 2,

  and thereby forming a first layer on the support material.

  On the first layer, a liquid containing an agent is applied

253975 1

  in an amount of between 0.1 and 30% by weight, by one of the coating processes mentioned above and then

  drying and thus prepares a recording medium for the use of

in the invention.

  The recording medium which is prepared by the process just described or by impregnation of the support material with a treatment agent is then subjected to calendering at temperatures between 50 and 200 C, preferably between and 120 C , with application of a pressure of between 100 and 1500 N / cm, preferably between 500 and 800 N / cm, which allows

  to improve the results of the recording medium.

  The following examples illustrate modes of setting

  of an ink jet recording method according to the present invention.

invention:

EXAMPLE 6

  A mixture of the following components is heated to 70 ° C., stirred until completely dissolved and then filtered twice through a filter membrane having an opening of mesh.

  0.45 rm; an aqueous ink n 6 is thus prepared for recording

  Ink-jet recording according to the invention, Coloranc (1) of Table 1 (M = Na) Glycerol Diethylene glycol Sodium dehydroacetate Sodium thiosulfate Ethylenediamine tetraacetate Sodium ion-exchanged water% by weight 3.0 O , 16.5 0.2 O, 01 0.01 74.78 A mixture of the following components is dispersed in

  a ball mill for 10 hours, so as to prepare a dispersion of

  if we. Calcium Carbonate Powder Aluminum Hydroxide Powder Styrene-Butadiene Copolymer Latex (Solids) Ion Exchange Water% by Weight

2539751.

  The dispersion thus prepared is applied to a sheet of high quality paper having a thickness of 80 μm by means of a doctor blade with a solids deposit of 13 g / m 2 and then dried at 120 ° C. for 5 minutes. thus forms on paper a base layer for the recording layer. On this base layer, a 6% aqueous solution of aluminum chloride is applied by an air knife coating process, with a wet coating of 30 g / m 2 and the solution applied is then dried. 1100 C for 10 min: thus preparing a recording medium This recording medium is then subjected to calendering at 650 C with application of a pressure of 650 N / cm: thus preparing a recording medium jet

  of ink to be used in the present invention.

  Inkjet printing is performed on this recording medium using the aqueous ink NO 6 prepared above according to the invention and the aqueous ink and the printed images are subjected to the following tests (1). sharpness of the image and drying of the image The ink is passed through a nozzle with an internal diameter of 301 m with pulsations of a frequency of 100 k Hz which break the ink stream into isolated droplets which then strike a high-quality commercial paper sheet. This results in sharp images. The time required for the drying of the printed image is not more than 10 S at the temperature.

ambient and at normal humidity.

  (2) Retention test: Samples of the ink are sealed in glass containers and subjected to the following storage tests at -20 C for 1 month; b storage at 40 C for 1 month, c storage at 200 C for 1 year; and

  storage at 900 C for one week.

  There is absolutely no observation in the separation storage of pre-

  In addition, we do not detect any variations

  properties or color of the ink.

2539751.

  (3) Stability test of ink droplet ejection.

  Ink jet printing is performed as in the image sharpness and image drying test described above continuously for 1000 h. There is no sign of clogging of the image. nozzle or variation of the ejection direction of the ink droplets; on the contrary, a stable record is maintained.

  (4) Droplet ejection response test.

  After inkjet printing as described in (1), the apparatus and the ink are allowed to stand at ambient temperature and humidity for one month, after which they are used again to perform the inkjet recording in the same

  conditions described previously in (1) As in (3) above

  above, there is no variation in ejection stability

ink droplets.

  The above test is repeated in the same manner except that the apparatus and the ink are allowed to stand at 40 ° C. and 30% relative humidity for 1 week, instead of temperature and humidity.

  for a month again, there is no change in

  the stability of the ejection of the ink droplets.

  (5) Evaluation of the color of the images.

  The color of the images is evaluated by means of the hue error and the gray hue according to the GATF color evaluation method.

  (6) Water resistance of images.

  The water resistance of the images is measured by immersing the recording medium carrying the printed images in water at 300 ° C. for 1 minute and measuring the variation in the density of the images.

  images, from which the attenuation rate is deduced.

  (7) Resistance to light images.

  The images are exposed to the light of an arc lamp

  good for 6 h The attenuation rate of the images is calculated according to the following formula (reflected image densities) Variation of the image density 2 100 Initial image density The above test results are represented

in Table 3.

2539751.

EXAMPLE 7

  A mixture of the following components is heated to 700 ° C., stirred until completely dissolved and then filtered twice on a 0.25 μm filtering membrane: an aqueous ink 7 is prepared for the jet recording. of ink according to the invention. % by weight Color (1) of Table 1 (M = Li) 4.0 Glycerol 10.0 Diethylene glycol 20.0 "Deltop 33" (from Takeda Chemical Industries, Ltd) 0.5 Ion-treated water 65.5 A 5 wt% aqueous solution of polyvinylpyridine bromide was applied to an inkjet printing sheet (sold by Mitsubishi Paper Mills, Ltd) by a coating process with a blade of air with a deposit of 0.5 g / m 2

  to dryness and the sheet is then dried at 120 ° C. for 5 minutes:

  thus, an inkjet recording medium n 2 for the use of

in the invention.

  Inkjet printing is performed on this recording medium using the aqueous ink No. 7 prepared above according to the invention and the aqueous ink and the same test images are subjected to example 6 The results obtained are indicated in the

table 3.

EXAMPLE 8

  A mixture of the following components is heated to 70 ° C., stirred until completely dissolved and then filtered twice on a 0.451 μm filter membrane: an ink is thus prepared.

  No. 8 for the ink jet recording according to the invention.

  % by weight Color (1) (M = Na) 6.0 Diethyleneglycol 12.0 Glycerol Triethanolamine "Hokucide LX-2" (from Hokko Chemical Industry Co., Ltd) Ion-exchange-treated water 4.0, 0 0.5 72.5

253975 1

  A 3% by weight aqueous solution of octadecylammonium acetate is applied with a deposit of 0.6 g / m 2 dry on a sheet of ordinary paper with a degree of bonding of 1 S and

  with a thickness of 951 m: a recording medium is thus prepared.

  Ink Jet No. 3 for use in the invention. Inkjet printing is performed on this recording medium using the aqueous ink N O 8 prepared above

according to the invention.

  The aqueous ink and the printed images are subjected to the same tests as in Example 6 The results are reported

in example 3.

EXAMPLE 9

  A mixture of the following components is heated to 700 ° C., stirred until completely dissolved and then filtered twice on a 0.451 m filtering membrane: an ink is thus prepared.

  aqueous NO 9 for the ink jet recording according to the invention.

  % by weight Color (1) of Table 1 (M = K) 3.0 Glycerol 5.5 Diethylene glycol 16.5 Potassium dehydroacetate 0.2 Potassium thiosulphate 0.01 Potassium ethylenediaminetetraacetate 0.01 Water treated with potassium hydroxide The ink jet printing was carried out on the recording medium NO 1 prepared in Example 6 using the aqueous ink NO 9 prepared above according to the invention, and the ink was submitted. water and images obtained at the same tests as

  Example 6 The results are shown in Table 3.

COMPARATIVE EXAMPLE 4

  A mixture of the following components is heated to 70 ° C., stirred until completely dissolved and then filtered twice through a 0.251 μm filter membrane: a comparative aqueous ink 4 is then prepared for jet recording.

ink.

253975 1,

  Red Acid CI 92 Glycerol Diethylene glycol "Deltop 33" (from Takeda Chemical Industries, Ltd) Ion Exchange Water% by Weight 4.0, 0.0, 0.5, 5 ink on the same commercial inkjet printing sheet as used

in example 7.

  The comparative aqueous ink n 4 and the images obtained are subjected to the same tests as in Example 6 The results

  thus obtained are shown in Table 3.

TABLE 3

Example Example Example Example

6 7 8 9 compared

  tif 4 Sharpness drimage and sharpness of aget Good Vouchers Good Vouchers Good Drying Conservation Good Good Good Good Good Stability Ejection Good Good Good Good good drops of ink Answer ejection of ink drops Good Good Good Good Good ink drops Tint error 37 38 41 37 43 Tint gray 14 10 12 14 18 Water resistance 1, 3% 2.0% 1.8% 1.3% 48% Light resistance 3.2% 5.0% 2.4% 3.2% 38% As can be seen from the results shown

  in Table 3, the images printed on the recording media

  to be used in the invention are extremely resistant to water and

  in light compared with the comparative example.

EXAMPLE 10

  A mixture of the compounds is heated at 70 ° C. for 3 hours.

  Next, stir until completely dissolved and then filter twice through a filter membrane with mesh

  0.45, im: thus preparing an aqueous ink n 10 for recording

  very ink jet according to the invention.

  % by weight Color (18) of Table 1 3.0 Glycerol 5.5 Diethylene glycol 16.5 Sodium dehydroacetate 0.2 Sodium thiosulfate 0.01 Ethylenediamine-t, sodium traacetate 0.01 Pure water 74.78 Dispersed a mixture of the following components in

  a bead mill for 10 hours so as to prepare a dispersion of

  if we. Calcium carbonate powder Aluminum hydroxide powder Styrene-butadiene copolymer latex (solids) Casein% by weight Water 37 The dispersion thus prepared is applied to a sheet of high quality paper having a thickness of 801 mf 2 by means of an air space, with a deposition of 8 t of solids of 13 g / m 2 and then dried at 120 ° C. for 5 min.

  paper a base layer for the recording layer.

  On this base layer, a 6% aqueous solution of aluminum chloride is applied by an air knife coating process with a dryness of 1.5 g / m 2 and then dried. the solution applied at 110 ° C. for 10 min.

  recording medium. This recording medium is then subjected to

  At 65 ° C with application of a pressure of 650 N / cm, an ink-jet recording medium 4 is prepared for use in the invention. ink on this medium

  by using the aqueous ink n prepared below.

  according to the present invention, by passing the ink to

2539751,

  through a nozzle with an inside diameter of 301 m

frequency of 100 kHz.

  The aqueous ink and the images obtained are subjected to the same color evaluation, water resistance and light resistance tests as in Example 6. The results obtained are shown in Table 4 below. -after.

EXAMPLE 11

  A mixture of the compounds is heated at 70 ° C. for 3 hours.

  Next, stir until completely dissolved and then filter twice through a filter membrane with mesh

  0.251 m: thus preparing an aqueous ink n 11 l for recording

  very ink jet according to the invention.

  % by weight Color (20) of Table 1 4.0 Glycerol 4, O Diethylene Glycol 13.0 "Deltop 33" (Takeda Chemical Industries Co., Ltd) 0.5 Water treated with 78.5 ion exchange A solution is applied 5% aqueous polyvinyl pyridine bromide on an inkjet printing sheet

  (Mitsubishi Paper Mills Co., Ltd.) by means of a coating process

* tion to the air knife, with a depft of 0.5 g / m 2 dry and then the sheet is dried at 120 C for 5 min: thus preparing a medium

  ink jet recording system 5 for use in the invention.

  tion. Ink jet printing is performed on this recording medium using the aqueous ink prepared in the above manner.

  according to the invention, under the same conditions as in example 6.

  The aqueous ink and the images obtained are subjected to the same tests as in Example 6 The results obtained are indicated

in Table 4.

EXAMPLE 12

  A mixture of the compounds is heated at 70 ° C. for 3 hours.

  Next, stir until completely dissolved and then filter twice through a filter membrane with mesh

253975 1

  0.251 m: thus preparing an aqueous ink n 12 for recording

  very ink jet according to the invention.

  Dye (22) of Table 1 Diethylene Glycol Glycerol Triethanolamine "Hokucide LX-2" (Hokko Chemical Industry Co., Ltd) Ion Exchange Water% by Weight 6.0 22.0 6.0, 0.5, A 3% by weight aqueous solution of octadecylammonium acetate was applied with a dry deposit of 0.6 g / m 2 on a 1 S bonding grade plain paper sheet.

  95 μm thick: thus a recording medium is prepared.

  No. 6 for the use in the invention.

  Inkjet printing is carried out on this medium

  by using the aqueous ink n 12 prepared below.

  above according to the invention under the same conditions as in Example 6.

  The aqueous ink and the images obtained are subjected to the same tests as in Example 6 The results obtained are indicated

in Table 4.

COMPARATIVE EXAMPLE 5

  A mixture of the compounds is heated at 70 ° C. for 3 hours.

  Following these steps, the mixture is stirred until completely dissolved and then filtered twice through a filter membrane having a mesh size of 0.251 μm.

inkjet recording.

  Red Acid CI 92 Glycerol Diethylene glycol "Deltop 33" (from Takeda Chemical Industries, Ltd) Ion-exchange treated water% by weight 4.0 4.0 13.0 0.5 78.5 Printing is carried out inkjet on an inkjet printing sheet (from Mitsubischi Company

  Paper Mills, Ltd) under the same conditions as in Example 6.

  Comparative aqueous ink No. 5 and the images obtained are subjected to the same tests as in Example 11 The results

  obtained are shown in Table 4 below.

TABLE 4

  As can be seen from the results indicated

  in Table 4, the images printed on the dien-

  for use in the invention are much more resistant

  to water and light compared to the comparative example.

  It is understood that the invention is not limited to

  preferred embodiments described above as illustrative

  and the person skilled in the art may make various modifications and changes thereto without departing from the scope and expression

of the invention.

  Example Example Example Example 11 12 comparative Tint error '36 39 43 43 Water resistance 1.3% 2.5% 1.8% 48% Light resistance 2, 8% 1.9% 1.8% 38% 37 '

RE V E N D-I CA TI O N S

  I 1 Aqueous magenta ink for ink jet recording, characterized in that it consists of: (a) a water-soluble dye of formula

R R 1

-3

R '2

1

  in which R 1 represents hydrogen or an alkyl group, R 2 and R 3 each represent F (_P) or (M +

(R 3 N (R

  R 7 represents an alkyl group or an amino group, m is 0, 1, 2 or 3 and is not equal to 0, 1 or 2, represents an alkyl group or a halogen, p is 0, 1

6

  or 2, R represents 503 or C 00, R represents hydrogen, -503 M or halogen, q is 0, 1 or 2 and M represents an alkali metal cation, an amine cation or an ammonium ion ; (b) water and

(c) a humectant.

  An aqueous ink according to claim 1, characterized

  in that said alkali metal cation is selected from Na +, Li and K.

  3 -Aqueous ink according to claim 1, characterized

  wherein said amine cation is selected from f (2 CH 2 CHOH) 3 ,.

t H (CH 2 H 5) 3.

  Aqueous ink according to claim 1, characterized

  in that said humectant is selected from polyalcohols

and their alkyl ethers.

  An aqueous ink according to claim 1, characterized in that said humectant is a mixture of glycerol and

diethylene glycol.

  Aqueous ink according to claims 4 and 5,

  characterized in that the amount of said humectant is from 30% to the total weight of said aqueous ink.

  Aqueous ink according to claim 5, characterized

  in that the glycerol / diethylene glycol mixture ratio is

  in the range of 1/1 to 1/5.

  An aqueous ink according to claim 4, characterized

  in that said polyalcohols are selected from ethylene-

  glycol, diethylene glycol, triethylene glycol, propylene glycol,

  glycerol, polyethylene glycol and polypropylene glycol.

  An aqueous ink according to claim 4, characterized

  in that said polyhydric alkyl ether ethers are selected from the following: ethylene glycol monoethyl ether, ether

  monobutyl ethylene glycol, diethylene methyl ether

  glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether and

  monoethyl ether of triethylene glycol.

  Aqueous ink according to claim 1, characterized

  in that it further comprises a soluble preservative

  in water and a mildew agent.

  An aqueous ink according to claim 1, characterized

  in that it further comprises an agent increasing the solubility

  said dye in said ink selected from triethanol-

  N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-

  imidazolidinone, valerolactone, caprolactone and acetate

  of ethylene glycol monomethyl ether.

  An aqueous ink according to claim 1, characterized

  in that it also comprises a screw adjusting agent

cosité.

  An aqueous ink according to claim 1, characterized

  in that it further comprises a pH adjusting agent capable of adjusting the p H of said aqueous ink in the range of

9.0 to 11.0.

  Method for recording the ink jet image on a recording medium containing at least one

  component chosen from water-soluble salts of di or poly-

  alkylamine salts, quaternary ammonium salts, compounds having two or more amino groups, compounds having two or more amido groups and basic polymeric products, characterized in that an aqueous ink is used.

claim 1.

  Recording method according to the claim

  characterized in that the amount of said water-soluble metal salt in said recording medium is 0.2 g / m 2 or more.

  16 Recording method according to the claim

  14, characterized in that the amount of said alkylamine salt

  contained in said recording medium is 0.05 g / m 2 or more.

  17 Recording method according to the claim

  14, characterized in that the amount of said quaternary ammonium salt contained in said recording medium is

0.1 g / m 2 or more.

  18 Recording method according to the claim

  14, characterized in that the amount of said compound having two or more amino groups or two or more amido groups

  contained in said recording medium is 0.05 g / m 2 or more.

  19 Recording method according to the claim

  14, characterized in that the amount of said basic polymeric product contained in said recording medium is 0.05 g / m 2

or more.

  Recording method according to the claim

  14, characterized in that said water-soluble metal salt is selected from Mg C 12, Ca Br 2, Ca C 12, Ca (N OO) 2, Ca I 2, Zn C 12, Zn Br 2, Zn I 2, Zn (C 103) 2, Zn 504, Zn (N O 3) 2, Sr I 2, Sr Br 2, Sr C 12, Sr (N OO) 2, Ba C 12, Ba (N OO) 2, Ba (OH) 2, Ba I 2, Ba Br 2, Fe (N 3 O) 2, Ni (N O 3) 2, Ni SO 4, Ni C 12, Cu C 12, Cu SO 4, A 1 C 13, A 12 (SO 4 ) 3, Al (N 03) 3, Sc C 13, Sc (N O 3) 3, Sc 2 (504) 3, Ga (NO) 3 Ga C 13, Ga 2 (504) 3, In C 13, Fe ( N 03) 3, alums, TC 4 Ge C 14

  Zr (504) 2, Sn C 14, Sn (504) 2 and Pb (CH 3 C 00) 4.

  21 Recording method according to the claim

  14, characterized in that said alkylamine salt is selected

253975 1

  among the following: decylammonium acetate, undecylammonium acetate, acetate

  docecylammonium, tridecylammonium acetate, tetradecyl acetate

  ammonium, pentadecylammonium acetate, hexadecylammonium acetate, heptadecylammonium acetate, octadecylammonium acetate, acetate

  of nonadecylammonium, eicosylammonium acetate, decyl chloride

  ammonium, undecylammonium chloride, dodecylammonium chloride, tridecylammonium chloride, tetradecylammonium chloride, pentadecylammonium chloride, hexadecylammonium chloride, heptadecylammonium chloride, octadecylammonium chloride, chloride

  of nonadecylammonium and eicosylammonium chloride.

  The recording method according to claim 14, characterized in that said quaternary ammonium salt is selected from the following:

  lauryltrimethylammonium bromide, lauryltrimethylammonium chloride

  monium, cetyltrimethylammonium bromide, cetyltrimethyl chloride

  ammonium, hexadecyltrimethylammonium bromide and

  decyl. The recording method according to claim 14, characterized in that said compound having two or more amino groups is selected from the condensation products of o or p-toluidine and formaldehyde, the epichlorohydrin adducts and

  of ethylenediamine and aminobenzoate derivatives.

  Recording method according to claim 14, characterized in that said compound having two or more groups

  amindo is selected from menthol derivatives.

  A recording method according to claim 14, characterized in that said recording medium is impregnated with at least one component selected from said water-soluble metal salts, said alkylamine salts, said ammonium salts, said compounds having two or more several amino groups, said compounds having two or more amido groups and said

basic polymer products.

  The recording method according to claim 14, characterized in that said recording medium comprises a layer which contains at least one component selected from said water-soluble metal salts, said alkylamine salts, said quaternary ammonium salts, said compounds having two or more amino groups, said compounds having two or more amido groups and said basic polymeric products.