JPS6285983A - Recording medium and recording method - Google Patents

Abstract

PURPOSE:To enhance color development properties, light resistance and water resistance, by incorporating a nonvolatile amine into a silica-containing recording medium. CONSTITUTION:This recording medium comprises a base consisting of an ordinary paper, a converted paper, a synthetic paper, a plastic film or the like, with silica and a nonvolatile amine provided in or on the base. Silica is preferably a synthetic fine particulate silica having a specific surface area measured by the BET method of at least 100m<2>/g. The nonvolatile amine is an amine which does not contain an alcoholic hydroxyl group, has a molecular weight not considerably small and is substantially nonvolatile at normal temperature. To incorporate silica and the nonvolatile amine into the base, for example, the two components may be added simultaneously or separately in the process of making a paper for obtaining the base. A recording medium of the type in which the two components are contained in a coated layer on the surface of the base can be produced by adding the two components to a coating liquid, applying the resultant coating liquid to the base, and drying the applied liquid. With the nonvolatile amine incorporated into a silica-containing recording medium, the light resistance of the medium can be markedly enhanced without loosing the excellent color development properties inherent in the silica-containing recording medium.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a recording medium and a recording method, and more specifically to a recorded image that has one characteristic such as excellent color development, luminosity, and water resistance. The present invention relates to an improved inkjet recording medium and an inkjet recording method using the medium.

(Prior art) Inkjet recording methods employ various recording liquid (referred to as ink) ejection methods (for example, electrostatic suction method, method of applying mechanical vibration or displacement to ink using a piezoelectric element, and method of applying mechanical vibration or displacement to ink using a piezoelectric element). (methods such as foaming by foaming and using that pressure, etc.)
This method generates small droplets of ink, makes them fly, and makes some or all of them adhere to a recording medium such as paper to perform recording, but it generates less noise and
It is attracting attention as a recording method that allows high-speed printing and multicolor printing.

Water-based inks are mainly used for inkjet recording in terms of safety and printability.

-On the other hand, conventional paper has generally been used as a recording medium. When recording on such paper using liquid ink, it is generally necessary that the ink does not bleed onto the recording medium and cause the print to become blurry, and that the ink dries as quickly as possible after recording. It is desirable not to accidentally contaminate the paper surface.

In other words, in the inkjet recording method, (1) Even if the ink is quickly absorbed into the recording medium, the ink deposited later may mix with the ink deposited earlier, disturb the ink dots, or flow out. (2) The ink droplets must not spread on the recording medium and the diameter of the ink dots must not become larger than necessary; (3) The shape of the ink dots must be close to a perfect circle and the surrounding area must be smooth. .

(4) The density of the ink dot is high and the area around the dot is not blurred.

(5) The white color of the recording medium is high and the contact with the ink dots]
・Large [...] (6) The color of the ink does not change depending on the recording medium; (7) There are few dimensional changes (e.g. wrinkles, spread) of the recording medium before and after recording; needs to be met.

By the way, since conventional inkjet recording methods mainly use water-based inks, there is a problem that the recorded images lack water resistance, and when exposed to water, the ink bleeds and characters become illegible. It was also required to do so.

For example, the ink-ciendo recording medium described in Japanese Patent Application Laid-open No. 56-99693 contains a quaternary ammonium halide and the like to provide water resistance of 4=j. However, it has been recognized that such measures to improve water resistance have the disadvantage that the light resistance of the recording agent (dye, etc.) is significantly reduced.

In addition, paper containing silica has been proposed as an ink-end recording medium, and this recording medium has various advantages as an ink-end recording medium, such as excellent color development of the recording agent. , a water-soluble dye in the medium;
In particular, when recording is performed with ink using a direct dye, acid dye, or food coloring agent as a recording agent, there is a disadvantage that the formed image has poor light resistance and discolors and fades, although the reason is not clear.

(Problems to be Solved by the Invention) An object of the present invention is to satisfy all the problems that the prior art could not solve in the above-mentioned technical field. In particular, the present invention aims to simultaneously improve the various requirements listed in Section 1F in recording images using the inkjet recording method, particularly color development, light fastness, and water resistance. 1. Improving the light resistance of images when using silica-containing recording media that have poor light resistance.
The goal is to make people feel better.

Another object of the present invention is to provide a novel inkjet recording medium and recording method that can consistently exhibit excellent recording properties even when using a wide variety of water-based inks containing water-soluble dyes.

-[Bipedal and other objects are achieved by the invention below.

(Disclosure of the Invention) That is, the present invention consists of two inventions, the first invention being a recording medium characterized by having both silica and a nonvolatile amine, and the second invention being a recording medium characterized by containing silica and a nonvolatile amine. This is a recording method characterized by recording on a recording medium containing both silica and a non-volatile amine using an ink containing a water-soluble dye as a solvent.

Next, to explain the present invention in more detail, the main feature common to the present invention is that it can be used with various recording media, especially those that conventionally provide images with excellent color development, but the light fastness of the images is insufficient. By adding a non-volatile amine to a silica-containing recording medium, the light fastness of images formed with ink, especially ink containing water-soluble dyes, can be significantly improved while maintaining the excellent color development properties. This is a point that has been discovered, and the present inventor has achieved the object of the present invention based on such knowledge.

Next, to explain the recording medium that mainly characterizes the present invention, the recording medium of the present invention is characterized by combining various conventionally known recording media with a specific compound, that is, silica and a nonvolatile amine. , With such a configuration, [1] of the present invention is achieved.

The recording medium of the present invention is obtained by using various conventionally known recording media such as plain paper, processed paper, synthetic paper, and plastic film as a base material, and by making the base material contain silica and a nonvolatile amine.

As the silica used in the recording medium of the present invention, any conventionally known natural or synthetic silica as a filler can be used, but particularly preferred ones have a specific surface area of 100 rn2/g or more by the BET method. Preferably lOO~
700 m'/go') is a synthetic fine particle silica, and by using silica with such a specific surface area, it is possible to achieve rich color development of the water-soluble dye in the ink, and optimal ink dot shape and size. be able to.

In addition, the nonvolatile amine used in the present invention is an amine that does not contain an alcoholic hydroxyl group, and has a molecule rl: beyond a certain level, and is substantially nonvolatile at room temperature, so long as it is aromatic, aliphatic, Any conventionally known nonvolatile amine can be used, regardless of alicyclic group.
For example, preferred examples include undecylamine, F-decylamine, tridecylamine, stearylamine, oleylamine, octamethylenecyamine, nonamethylenediamine, decamethylenediamine, polyoxyethylenealkylamine, hexamethylenetetramine, tetraethylenepentamine, etc. Among these, particularly preferred are water-soluble to hydrophilic nonvolatile amines such as hexamethylenetetramine and polyoxyethylene alkylamine.

Any method may be used to incorporate silica and non-volatile amine into the base material as described in Section 8H, but for example, these two components may be added simultaneously or separately in the paper making process of such a base material to make paper. Alternatively, there is a method 7 in which these two components are added to a paper impregnating liquid and the S material is immersed in the post-treatment method, but either method may be used.

In such a method, the amounts of the two components added to the recording medium are such that the silica accounts for about 5 to 30 parts by weight and the nonvolatile amine accounts for about 0.05 to 10 parts by weight in 100 parts by weight of the recording medium. It has been found that the uninvented object is best achieved by doing so. Although it is effective to some extent even outside these ranges, there is a risk that the balance between color development and light fastness of the formed image will be lost.

On the other hand, in the recording medium of the present invention of the type that contains the above-mentioned two components in the coating solution on the surface of the substrate, the above-mentioned two components are added to the coating solution for the substrate such as paper, and this coating solution is It is manufactured by coating Murakami and drying it. Other components of the coating solution in this case include conventionally known inorganic pigments such as clay, talc, diatomaceous, WM calcium, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, satin white, aluminum silicate, and lithopone. Types: Water-soluble polymers such as starch, ceratin, casein, gum arabic, sorta alginate, carboxymethyl cellulose alcohol, polyvinylpyrrolidone, and sodium polyacrylate; synthetic rubber latte.

Synthetic resin latex such as alcohol; polyvinyl butyral,
Polyvinyl chloride! Organic solvent-soluble resins such as: and dispersants, fluorescent dyes, etc. PH adjuster, antifoaming agent, lubricant,
Various additives such as preservatives, surfactants, and waterproofing agents can be mentioned.

The solid content of the coating solution is preferably about 1 to 50 tons%, and the coating solution is usually coated by a known L method such as a roll coater method, a blade coater method, an air knife coater method, etc. A film of about 1 to 50 g/m' (dry coating) is applied to the base material. Preferably 2-30
Apply approximately g/m' (dry coating amount -).

Conventional recording media, especially recording media used in the ink side recording method, are known to be silica-containing recording media or those that exhibit excellent color development with ink. However, according to the present invention, when recording is performed with ink made of water-soluble dye, the light fastness of the formed image is extremely low.However, according to the present invention, a nonvolatile amine as described above is added to the silica-containing recording medium. As a result, the light fastness, which had been a drawback of silica-containing recording media, can be significantly improved without losing any of the excellent color development properties inherent in silica-containing recording media.

, 4i: The second invention is an invention of an inkjet recording method using the recording medium of the invention as described above,
Any conventionally known ink can be used as the ink used in the recording method, as long as it contains a water-soluble dye.

As the water-soluble dye that is an essential component of the ink used in the inkjet recording method of the present invention, water-soluble dyes such as direct dyes, acid dyes, and food colorings are preferably used.

For example, direct dyes include c, r, direct bry') 2.4.9.11
．． 14, +7. 19.22.27.32.36.3
8.41. 48.49.5I.

56.62.71.74.75. 7? ,78.8o,
+05, +06. 107, 108,
112, +13. 117. 132. 148
．． 154, +94.

c, r, direct yellow 1.2.4.8.11
゜12.24.26.27.28.33.34.39.
41. 42.44.48, 50.51. 58, 72
．． 85.86.87.88.98, +00, +10
; (1:, 1. Tie Left Orange 8, 8, 10
．． 26.29゜39.41.4S, 51.102; c, r, Direct Red 1.2.4.8, 9.11
゜13.17.20.23.24.28.31.33.
37.39.44°46, 47.48.51.59, C
2, 63, 73, 75, 77, 8o, 81, 83.8
4.85.90, 94.99, +01, +08.
110, 145, +89, 197, 220
, 224 , 225 .

226, 227, 230; C, 1, Direct eye left 1.7. &
, 12.35.48.5L90.94; c, r, Direct Blue 1.2. +3.8.15
．． 22.25.34.69.70.71.72.75.
76.78.8o, 81.82.83.86.9o, 9
8, 106. 108, +1°120,
123, 158. 1133. 185,
192, 193. 194, 195,
+98. 199. 200. 201. 202.
203, 207, 218, 238
, 23? , 239, 24B.

258; C01, Direct Green l, 8, 8, 28.3
3.37, 63, 64; C, 1, Direct Brown IA, 2, 8, 2
5.27.44.58.95.100, 10+,
108, 112, 173゜194.195
．． 209.210, 2+1.

As acid dye 1, C, 1, acid black 1.
2.7.1&, 17.24.28.28.31.41.
48.52.58.60.63. 94. 107,
109, 112, 118.

119, 121, 122, 131, 155
, 158.

C, 1, acid yellow 1. 3.4.7. ll,
12.13.14.17.18, +9.23.25.2
9.34.36.38.40.41.42.44.49
．． 53.55.59.61. Ha,? 2.7B, 78.9
9, Ill, 114, 116.122.13
5, 181, 172; C, 1,7 Gid Orange 7.8, lo, 33.56
゜64; c, r, reed, dread 1.4, 8, 8, +
3.14.15, 18, 19.21.28.27. 3
0.32.34.35. 37°40, 42.51.
52.54.57. 80.82. 83.85.87
゜88.89, C2, 94, 97, 106, 108, 1
10, 1+9, +29, 131, 13
3, 134, 135, 154. 15
5. 172, 176, 180, 18
4, +88, 187. 243.

249, 254, 256, 2B0
, 289, 317, 318.

C,! , reeds, dough 7.11.15.
34.41, 43, 49.75; c, r, reed, dobro 1, 7.9, 22.23
．． 25°27.29.40.41.43.45.48.
51.53. 55.5G, 59, 62. 78, 80
．． 81.83.90.92.93, 102.

104, 111, 113, 117
, 120 , 124 , 128 .

+45, 1137, +71. 175,
183, 229, 234. 236; C, 1,7 Gid Green 3.9, 12. +6.
19.2o, 25.27, 41°C, 1, Asindo Brown 4.24; Furthermore, as food colorants, C, 1, Food Black 2: C, 1, Food Yellow 3.4, 5; c, r,
Hood Red 2.3.7.9.14.52.87.92
．． 94.102, 104, +05.108
.

c, r, Food Eye Iolet 2:C,1, Food Blue I, 2:C,1, Food Green 2.3, etc., but are not limited to these, of course.

These water-soluble dyes are generally used by being dissolved in water or a liquid medium consisting of water and an organic solvent, and the liquid medium components preferably include water and various organic solvents. Although a mixture may be used, it is preferable to adjust the water content in the ink to be within the range of 20 to 90%.

Examples of the water-soluble organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 5ec-
Butyl alcohol, tert-butyl alcohol, isobutyl alcohol.

Alkyl alcohols having 1 to 4 carbon atoms; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyethylene glycol and polypropylene glycol polyalkylene glycols such as ethylene glycol, propylene gelylcol, 1,2,6-hemosantriol, thioglycol, hexylene glycol, diethylene glycol, etc. with 2 to 6 alkylene groups
Glycerin: Lower alkyl ethers of polyhydric alcohols such as ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, and triethylene glycol monomethyl (or ethyl) ether. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether are preferred. Polyhydric alcohols are particularly preferred because they are highly effective as wetting agents to prevent nozzle clogging caused by evaporation of water in the ink and precipitation of water-soluble dyes.

A solubilizer can also be added to the ink. Typical solubilizers are nitrogen-containing heterocyclic ketones, and their intended action is to dramatically increase the solubility of water-soluble dyes in liquid media. It's about improving.

For example, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone are preferably used.

Ink prepared from such components has its own recording properties (signal response, droplet formation stability, ejection stability,
It is excellent in long-term continuous recording performance, ejection stability after long-term recording material IE), storage stability, and stability to recording media, but in order to further improve these characteristics, Various additives may also be included. Viscosity modifiers such as water-soluble resins such as polyvinyl alcohol and cellulose;
Examples include various cationic, anionic or nonionic surfactants; surface tension regulators such as diethanolamine and triethanolamine; pH regulators using buffer solutions; and the like.

Further, in order to formulate an ink used in an inkjet recording method in which the ink is charged, a resistivity adjuster such as inorganic salts such as ammonium lithium lithium chloride and sodium chloride is added. Note that when applied to an inkjet recording method in which ink is ejected by the action of thermal energy, thermal physical property values (eg, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted.

In the method of the present invention, the inkjet recording method for performing recording by applying the above-mentioned ink to the above-mentioned recording medium is a method in which the ink can be effectively removed from a nozzle and the ink can be applied to the recording medium, which is a projectile. Any method may be used, and a representative example of such methods is 1, for example, IEEE Trans Accordion on Industry Applications.
tions onIndustry Application
ions) Vat, IA-13, No. 1 (1
February/March 977 issue) 1 Nikkei Electronics 197
April 19, 1973 issue, January 29, 1973 issue and 19
It is listed in the May 6, 1974 issue. The methods described above are suitable for the method of the present invention.To explain some of them, there is an electrostatic attraction method, in which:
Place the nozzle several layers in front of the nozzle.1. ) A method in which a strong electric field is applied between the ink and the accelerating electrode, the ink is turned into particles and drawn out one after another from the nozzle, and while the drawn out ink flies between the deflection electrodes, an information signal is given to the deflection electrode and recorded; There is a method of ejecting ink droplets in response to an information signal without deflecting the ink droplets, and either method is effective for the method of the present invention.

The second method is to forcibly eject minute ink particles by applying high pressure to the ink with a small pump and mechanically vibrating the nozzle with a crystal oscillator. At the same time as the injection, it is charged according to the information signal. When the charged ink particles pass between the deflection electrode plates, they are deflected according to band'+j+IIY. Another method using this method is called the microdot inkjet method. In this method, ink pressure and excitation conditions are kept within a certain range of appropriate values, and two types of ink droplets, large and small, are ejected from the nozzle tip. Only small and medium diameter droplets are generated and used for recording. The feature of this method is that it is possible to obtain a group of minute droplets even with a nozzle diameter as large as conventional ones.

A third method is a piezo element method, in which a piezo element is used as a pressure means for applying pressure to the ink, rather than a mechanical means such as a pump as in other methods. This method applies an electric signal to a piezo element to cause mechanical displacement, thereby applying pressure to the ink and ejecting it from a nozzle.

In addition, an inkjet method is disclosed in Japanese Patent Application Laid-Open No. 54-51837, in which ink subjected to the action of thermal energy undergoes a sudden change in volume, and the acting force due to this state change causes the ink to be ejected from a nozzle. can also be used effectively.

According to the present invention as described above, it is possible to provide an image that simultaneously has significantly superior color, color development, and light fastness compared to the conventional method using a recording medium.
In particular, by using ink made of direct dyes, acid dyes, or food colorings, it is possible to provide images that simultaneously have excellent quality, particularly excellent color development and light fastness, to a degree not seen in conventional examples. I can do it.

Furthermore, according to the present invention, the ink is quickly absorbed into the recording medium, and even when ink of different colors is repeatedly deposited on the same spot within a short period of time, there is no ink flow or oozing phenomenon, and high resolution can be achieved. A clear image can be obtained. Therefore, the recording medium and recording method of the present invention can be used not only for general recording but also for
It is particularly suitable as a recording medium and recording method for inkjet recording.

Hereinafter, the present invention will be explained in more detail according to Examples and Comparative Examples. However, parts or percentages in the text are based on weight unless otherwise specified.

Example 1 As a base material, the size degree based on JISP8122 is 35
A dry coating amount of LOg/rrr' of general high-quality paper (64 g/rrr') with the following composition was applied onto this base material.
The recording medium of the present invention was obtained by coating with a blade coater in the proportion of For comparison, a coating solution containing no non-volatile amines was prepared.
This was coated in the same manner as a recording medium of a comparative example.

Synthetic silica (Fuji Davison Chemical, Cyroid 404
, specific surface area 340g/g) 100 parts polyvinyl alcohol (manufactured by Kuraray, PVA117)
50 parts non-volatile amine
X part water
An inkjet recording method was performed using the following ink on a 400-copy recording medium, and the light resistance of the solid printed portion of the resulting image was evaluated.

Light resistance is measured using a xenon fade meter for 30 hours of irradiation (4
0°C, 65%RH 155mW/crn') L, Using a high-speed spectrophotometer model CA-35 (Murari Color Technology Research Institute), determine the color difference (ΔEab wood) from the unirradiated one and measure the light resistance. And so. The smaller the value, the better the light resistance.

The results are shown in Table 1 below.

C, 1, Food Black 2 2 parts diethylene glycol 15 parts polyethylene glycol 18 parts water
70 copies--12,7
(Comparative example) Hexamethylene tet 0.5 9.9 (Example) Lamin hexamethylene tet) 2.0 8.9 (Example)
Lamin hexamethylene lenticule 5.0 5.8 (Example) Lamin hexamethylene lenticule, 0 4.0 (Example) Lamin polyoxyethylene 5.0 B, 3 (Example)
Oleylamine polyoxyethylene 5.0 5.9 CExample) Dodecylamine injection...Additive clay (X part) II...Light resistance (ΔEab book) As shown in Table 1 above, the recording medium of the present invention The light fastness of the recorded image obtained by the method of the present invention using a water-based ink containing a water-soluble dye was significantly improved compared to that of the comparative example. However, the ink did not bleed, and the image was clear and high-resolution. Note that the color development properties were equally excellent in the Examples and Comparative Examples.

Example 2 Freeness (C, S, F,) 400m as a raw material valve
J1 LBKP was used, and synthetic silica (Nippon Silica, Nip Seal NS, specific surface area 160r) was used as a filler.
rr''/g) was 39% by weight based on the solid content of the valve, and 0.2% by weight of cationic starch (CATOF, manufactured by Tamago National) as a retention aid was also based on the solid content of the valve.
This was added internally, and paper was made into a paper having a basis weight of 70 g/m' using a TAPPI standard sheet former to obtain a base paper.

Next, using a solution having the following composition as a coating liquid, the base paper was coated using a size press apparatus so that the dry coating amount was 2.0 g/m' to obtain a recording medium of the present invention. Further, a recording medium of a comparative example was prepared by coating a coating liquid containing no nonvolatile amine in the same manner as above.

Polyvinyl alcohol (manufactured by Kuraray, PVAC3T)
3-part non-volatile amine
2 parts water
Inkjet recording was performed on a 95-part recording medium using the following ink, and the light resistance and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 2.

C, 1, Direct Black 146 2 parts glycerin 15 parts polyethylene glycol 15 parts water
70 parts - 8,8 (Comparative example) Hexamethylenetet 5.3 (Example) Lamine polyoxyethylene 3.9 (Example) Oleylamine polyexyethylene 4.8 (Example) Dodecylamine As shown in Table 2 above The light resistance of images obtained by the method of the present invention using the recording medium of the present invention was significantly improved compared to that of the comparative example.

Example 3 The present invention was carried out in the same manner as in Example 1 except that 2 parts of polyoxyethylene oleylamine was used as the nonvolatile amine and the silica shown in Table 3 below was used. As shown in Table 3, specific surface area 100
In the case of silica of m''/g or more, light fastness was at a good level, high color density was exhibited, and excellent color development was exhibited.

80 1.05 7.4 100 1.31 7.5265
1.40 7.3340 1.50
7.3500 1.52 7.4 Note: Color development (expressed as black color density O1D) ■... Light resistance (ΔEab) Example 4 Example In place of the black dye in the ink in Example 1, Direct Yellow 86, Direct Blue 86, and Acid Red 35 were used to prepare yellow ink, cyan ink, and magenta ink, and these inks were used in Examples 1 to 3. As a result of performing inkjet recording in the same manner as in the above, excellent results almost the same as those of Examples 1 to 3 were obtained.

Claims (5)

[Claims] (1) A recording medium characterized by containing both silica and a nonvolatile amine. (2) Silica has a specific surface area of 100 m^ by BET method.
2/g or more of synthetic fine particle silica. The recording medium according to claim (1). (3) A recording liquid containing a water-soluble dye as a recording agent can be used to record a recording medium containing both silica and a non-volatile amine.
A recording method characterized by recording. (4) Silica has a specific surface area of 100 m^ by BET method.
2/g or more of synthetic fine particle silica. The recording method according to claim (3). (5) The recording method according to claim (3), wherein the water-soluble dye is at least one substance selected from direct dyes, acid dyes, and food colorings.