JPS5954593A - Ink jet recording method - Google Patents

Abstract

PURPOSE:To obtain an image having high resolution and clear and excellent color development by a method wherein a recording liquid of a specific water system is made to stick, by an ink jet method, onto a material prepared by forming on a supporting substance a layer which contains the particles of a filler and on which recording is to be made. CONSTITUTION:A coating liquid prepared by a method wherein the particles of a filler, such as silica, whose particle size is preferably about 1-30mum, and a binder such as polyvinyl alcohol, are dispersed in a medium and adjusted is applied onto a supporting substance, and thereby a material having a layer which is formed with the indefinite shapes of the particles of said filler appearing on the surface and on which recording is to be made is obtained. Then, the recording liquid whose water content is adjusted to be within 20-90wt% and which is introduced into minute holes is jetted from an orifice communicating with said minute holes so that it sticks onto said material whereon recording is to be made. Thereby a clear image is obtained without running or oozing of color even when another recording liquid of different color is made to stick onto the same place overlappingly.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for A;, =/L 7h recording, particularly for multicolor in/L7h recording.

The inkjet recording method uses various recording liquid ejection forces i((
For example, the recording liquid can be heated using the Shizuichi suction 1 method, the method of applying mechanical vibration or displacement to the recording liquid using a piezoelectric element, the method of heating the recording liquid to foam it, and using the pressure of the resulting pressure. Recording is performed by emitting small droplets of (ink) and making them fly, and some or all of them adhere to a recording material such as paper. ,
It is being used as a recording tool that can perform high-speed printing and multicolor printing.

Li-based water-based recording liquids are used as recording liquids for ink-side recording in terms of safety and printability.
As for the recording material C, conventional paper is commonly used.When recording using liquid liquid, general paper (this recording liquid is used as a recording paper) 1. It is safe to ensure that the printing does not bleed and become blurred, and it is also desirable that the recording liquid dries as quickly as possible after recording and does not stain the paper surface.

In the multi-color ink diant recording method using a different color recording liquid of Toriwage-6 Buddhist utensils 1-, l) the absorption of the recording liquid into the recording material is quick and the different color ink Sony Even if there is overlap, the recording liquid that was added later will be attached to the front. Also, it should not mix with the recording liquid, disturb the ink dont, or flow out, 2) The recording liquid should not spread on the recording material, and the diameter of the ink throat should not become larger than the required air flow L4. :3) The shape of the ink dont should be close to a perfect circle, and the surrounding area should be smooth; 4) The density of the ink dont should be high and there should be no shadow around the dot; 5) The color of the recording layer should be white. . Ink 1, To and 2" to and 2" to large 1'l, 6) The color of the recording liquid does not change depending on the recording material, V) -.1/ of the recording material. ), there are few fluctuations (for example, sagging, elongation) before and after recording, and there are certain things that satisfy the requirements of '9.

However, conventionally, in order to satisfy this
It depends on the characteristics of the recording material and recording liquid used.
It is understood that it is always big, but in reality it is small. In response to the various expenses required, the ink'n end record 1 no.

That is, for example, regarding the relationship between the recording material and the recording liquid, Jt
, I guess 1) It is used as office paper-1
．． When recording with ink 7.1 on page paper using a rated recording liquid (moisture content: about 70%), the ink absorption is poor and bleeding may occur; ]・1・The shape becomes significantly smaller than 7”. When this paper is also used for inkjet recording with a recording liquid that has a lower water content (less than 50% water content), the ink absorbency decreases. Although it is often rewritten, the chromaticity of the 1-ent shape is on the contrary low.Also, commercially available non-1-1 paper can be printed with ink) and recorded. - For absorption, 1 is water content 11 (despite #-1.) It exhibits the characteristics or the smear is thick.
F '71' 1 is inferior in shape and color. In addition, if you use ink and -71 recording on coated paper for printing, if you use a recording liquid with a high water content (70% or more of water), it will not be possible to print in a tont shape or ink. This is good, but the dot density is low and the ink absorption is very poor. On the other hand, liquids with low water content (more than 50% water) have good ink absorption, but the ink smearing is large and the ink concentration is low.

The first objective of the present invention is to solve all the problems in the technical field mentioned above that have not been solved by conventional techniques. The purpose of the present invention is to satisfy the requirements listed in -1. in recording a full-color image using a plurality of color recording liquids using an ink side recording force type.

Another object of the present invention is to use a recording liquid with a wide range of water content (4 to 7) (WiJ5, which can exhibit excellent recording characteristics).
In providing an LA (incident recording method) Item L-1 and other objectives I-1 are achieved by the present invention as described below.

That is, in the uninvented method, a recording liquid is injected into the pores from the opening 11 passed through the M11 company, and this recording liquid is applied to the support 1 i. - When the recording layer containing the filler <1'l-"f is placed in the recording month number, A. The ink used for recording by placing it on 1. -, 21. The recording power is The recording material is formed by the amorphous particle shape appearing on the surface of the recording layer, and the recording liquid has a moisture content of 2 9 )') :”if 9 0
This is an ink-send recording method in which 4 yen is used to indicate that the area is within the range of 4.

Inventiveness 7, the recording material used for odor is support 4.
, a Ni body and a recording layer coated on the surface thereof.

The support for the recording material may be paper (Is it appropriate to use paper?), porous material such as wood (9), wood (111), metal, crow, etc. Porous materials can also be used, and the choice of which one to use depends on the recording purpose and use.

The recording layer basically consists of a filler material 1' and a binder. For +J filler particles, 1" rows are ・Nlica, clay, talc, kuiso),,)^
Acid power +1, f & acid calcium 1, barium sulfate, titanium sulfuride, sulfur III! White inorganic pigments such as lead, sub/ice 7 points, aluminum resistant, SuI-Pon', alumina, and Theoty I-: Boris 1-1z 7
, 1 bottle, 1 urea-formalin resin, 1 poly
methacrylate, etc.
Polymer particles may be mentioned, and one of these may be used.

71. Scatter irregularly shaped particles of porous inorganic material on the surface of the coating layer. The particle size of the porous inorganic wood used is 30 units, Jz
Of course, it would be better if the ILLF was between 3 and 20 years old. Porous t1'? However, if the grain size of the machine face is too large and the grain is overcooked, the roundness of the throat will be distorted and the resolution of the recorded Bti image will be reduced, so it is not preferable. The recording layer number includes the full polar material particles 1, which have dye absorption properties of 10%, the more likely they are IJf, and the history number indicates the porous cell 1. structure. It's better to say that, ).,'l it, (Yo, 1 dye in the recording liquid '2 ~ Recording fullll or bti 4 added to the drum surface layer of the recording layer, T - force or 'I! Chromaticity? This is to make it better.

Ability, L7 γ1 reduction and Thea Boo 1, Sen-
)2, Kasein・, Arahiago J1.7, + Legire/
M:/-evening, methinolotylulose, 4mi 1
Nohininoshi/alcohol, polyhinirupi [Koriton,)
)5;,)-7ri1) No1/Sota, water-soluble t' of polyacrylamide, etc. is 2? = "6 'y) -f, Synthesis of synthetic Gototetenchus, etc. )Mesenlumemakuri-1・, Polyhinyl formal, Me】・Min resin, Polyamide, F□No J Shiki IBM, Po1 Know 1/
41 solvents such as tan, Alki 21, resin, etc. + 1 cedar]
One or more of these may be used.

Further, in the recording layer, a dispersant 1. ;i, ;, X, multiplication factor 1. It is also possible to mix various additives such as a PH adjuster, 1 pores, 1 IF, preservatives, and 1 r+'1 active+1'9.

The recording material of the present invention has the following characteristics:
Disperse the surface composition of these recording layers in a medium of water spray 9 (roll coating the prepared coating 1-7f) by one person, D
,, 1; Harkonai, 1 person, spray]-D/G method, -■Anaifini''-Teink method. be done. The combination ratio of filler particles and binder in Coating 1-Its and L7 are generally filler particles-r100Φ,
Hanabe ni't, J L-rH mackerel, l, agent force 0 no hb+o
oΦ,↑part is suitable, and when the average particle size of f- is large, it is possible to use less binder.Support The speed of the recording layer on the support is usually about 1 to 50 g/rn' (dry coating T amount) -1 applied to the support 1-1.Also, preferably about 2 to 30 g/m' IW (Dry application) – Early) Painting is best.

FIG. 1 shows approximately 15 yen of the surface of the recording layer of the recording material prepared in this manner and suitable for use in the recording method of the present invention.
This is a scanning electron micrograph taken at a magnification of 0.00 times, and its unique surface appearance is well-reduced. That is, the amorphous filling material 1' with a relatively large particle size, which is one of the components of the recording layer, appears on the surface of the recording layer in a randomly placed state, and the particles of In between, there are many large voids that function as ink absorption holes, and debris of various sizes are scattered, so to speak, creating an outward facing structure that could also be described as t-. Of course,
The filler particles -r appearing in Table 111j are also hardened by the binder and do not separate from the recording layer.

The original [! The recording liquid used in No. 11 consists of a recording agent and a liquid medium component such as a dye. The liquid medium component of the recording liquid may be a mixture of water and various water-soluble organic solvents, etc., or the content of water in the recording liquid may be between 30 and 9.
It is adjusted to be within the range of 0 tonne percentage. If the water content in the recording liquid exceeds 90% by weight, the affinity of the recording liquid to the surface of the recording material may be insufficient even if the above-mentioned recording material is used. The absorbency decreases, which increases the time it takes to fix the recording liquid and limits the recording speed. In addition, when there is overlap between recording liquids, mixing of recording liquids of different colors may occur, and the difference in color and color may occur. It is not appropriate because it will cause major expansion and disturbance.In addition, such a record is not appropriate because there is υ or υ. . Also, if the wood content in the recording liquid is less than 20 tons ψ%,
Even if the above-mentioned 1° recording material is used, the color quality, bleeding, and tonto shape will be poor, so it is not suitable for 1/I.

L-distribution water-soluble 41 solvents are used, for example, mayyl alniol, alcohol, n-noropyl alcohol, isopropyl alcohol, n-notyl alcohol, 5ec-bnal/luni, Alkyl alcohols having a carbon number of 1 to 4, such as 1-ru, tert-butyral: 1-ru, ・f-butyral, and the like; Amides such as Ruaya 1/Mido; Ketones such as acetone and diacetone alcohol; Polyanol glycols such as pyrene glycol; xylene glycol.

Pa/Echishi・2'kuri] - Noshi's alkylene group or 2~
Alkylene glycols containing 6 carbon atoms: glycerin 7; Jf lene glycol methyl (or ethyl), triethylene glycol methyl ( or ethyl)ether and other polyhydric alcohols.

Among these many water-soluble +14-iIa solvents, the polyvalent ? There are as many as 17 lower alkylnityls of polyhydric alcohols such as alcohol, triethylene glycol, monomethyl (or ethyl)elder, and the like. Polyvalent fluors can cause water in the recording liquid to emit water and cause the recording agent to precipitate! 1: This is particularly preferred because it is highly effective as a wetting agent to prevent clogging of nozzles.

A solubilizer can also be added to the recording liquid. Typical ii) Solubilization 611 contains atom-containing heterocyclic ketones C,
The purpose of this is to dramatically improve the solubility of the recording agent in the liquid medium.For example, N-methyl-2-picolidone, 1,3-cyme -Imitanrezo7'-- or Ilf is suitable for use.

A recording liquid prepared from such components has excellent recording properties (signal response ff1. droplet formation).
1. Long, u4. It is important to check the history of these characteristics, such as whether the recording bamboo has been used for recording materials for a long period of time (ejection stability after long-term recording material 11-1), retention f stability +1, or whether it has been crushed by one stone to the recording material. Contains additional additives to improve the appearance of the skin.
]-) Celluloses, viscosity modifiers for wood-soluble resin packs: famous surfactants for cationic, anionic or nonionic threads, jetanolamine, tri-1-tanolamine 29
Surface tension adjusting agent: 1]I (adjusting agent) by buffer solution can be mentioned.

In addition, in order to prepare the recording liquid used for the type of inkjet that carries the recording liquid, it is necessary to use inorganic substances such as lithium chloride, ammonium chloride, and sodium chloride 11. A resistivity adjuster such as Meng is added. In addition, when applying the recording liquid to the liquid jet system in which the recording liquid is discharged by the action of a thermal energy key, thermal physical property values (e.g., specific heat, thermal expansion -1 and coefficient 1.@den4+ etc.) may be adjusted.

,4. :9. According to Akira's method, even if different colored recording liquid adheres to multiple locations within a short period of time, there is no phenomenon of recording liquid flowing out or oozing out, and high-resolution 4-sharp, clear images can be obtained. A chromogenic image is obtained. Moreover, the ejection force type of recording liquid,
Recording I: Use a wide range of recording liquids on the target, etc. I5.
However, it is possible to exhibit the excellent characteristics of conventional technology, making it an excellent ink-end recording method for full-color recording.

Hereinafter, the method of the present invention will be explained in more detail according to the first part.

Example 1 Filler OSt (Toshi-C silica with Busil EI 50. Trade name, manufactured by Medama Silica Kogyo Co., Ltd., average grain J'-diameter.
A coating composition was prepared based on the composition described above using polyvinyl alcohol and SBR latex as a binder.

Silica 100 tons 11 parts Polyhydric alcohol 25 ttSBR Latinx 5 //Thursday
500 //- force, as a support, size IQ- based on JIS P8122 is 3
5 seconds general ten, page paper (J'P early 65 g / I'n
') [7, Coating 1-1-1-, I on this support 1-
ll 1-Dry coating on the surface of the eyes-■,-,Q-15g/
coated with plate coater V at a ratio of m';
A recording material was obtained by drying by the Hatake method.

FIG. 1 shows a scanning electron micrograph of the surface of the coating layer of the obtained recording material at a magnification of about 1500 times.

An on-demand type ink shed recording head (1!) ejects recording liquid onto this recording material using the following 6 types of ink using piezo vibration r~, output orifice diameter 50 mm, piezo vibration f-drive voltage 60V, frequency 4Kt
+z) 4) Using the recording yi setting, perform the I>resoet recording and evaluate the recording characteristics fi -) Daga Ink No. A (Composition) Glycerin 8 parts by weight Wood
90trC
,l Tie Kuto Blue 88 2/1 Ink No. B (J41 composition) Glycerin 28 Heavy-JII Part Water
70
trC,,l, direct blue 86 2
tt ink No. C (composition) Ethylene glycol 48 Volume wood
5Q
ttG, ■, Direct Blue B6 2 tt
Ink No., D (Composition) Diethylene glycol 20 parts by weight N-methyl-2-pyrrolidone 20 //Ethyl serotonin,
/ 23 tt tree
30 trC, 1, direct glue 88 2 tt ink NO, E
(Composition) Pa/Echire]/Glycol lOΦ, 1 part N-
Methyl-2-pyrrolidone 30/l ethyl cellosolve
38 //Wednesday
20 l/C1■, Girect Blue-862tt Ink No. F (Atl composition) Diethylene glyco-1110t T-,4,WN-Methyl-2-pyrroli F'7 4Q tt Ethylce U Solv 38tt Water
IQ //C, I evening (lz
Table 1 shows the evaluation results of Blue 86 2 tt recording characteristics. Each evaluation item 1 in Table 1 was measured according to the following method.

1) The density was determined by A'A using a Tensitometer PDM-5 (manufactured by Konishi Roku's Page Chogyo Co., Ltd.).

2) For the shape of the dot, the print was observed with a stereoscopic microscope, and a round shape was marked as 01. A slightly distorted circle was marked as △, and an irregular shape was marked as ×.

3) The degree of bleeding is determined by measuring the diameter of the printing tonnage using a stereomicroscope.
1, and the ink tromplet was small.

4) Color sharpness is determined by visually comparing the color sharpness of the ink-n-end recorded images, with the best one being 0, the best one being "!"
Let the problem be ×, and O. It was ranked as O, Δ, and ×.

5) Ink absorption is measured 1 second after printing 3 donts,
If there is no ink flowing out on the surface of the recording material and the image is bright, mark it as ○, otherwise mark it as ×.

Example 2 Using filler material 1' - carbonic acid 1, (iP average particle diameter 3IJn), binder 17, starch and SB
A coating composition was prepared based on the composition of M1 using R latte and alcoholic beverage.

) Father acid calcium 1. 1 0 0 Parts by Weight Starch 3Q ttSBR Tenx 101! water
300 //-・force, support Il
As an f-body, 7 (same as ground side 1, general 1-, γ'(
Using paper, the coating composition was coated on this support 1 at a dry coating rate of 20 g/m by the plate coating/no method, and dried by the printing method. 7 stars for record 44.

Using this recording material and the six types of recording liquids used in Example 1, the evaluation of recording characteristics was carried out in the same manner as in Example 1. The results are shown in Table 2.

Example 3 A composition for coating was prepared based on the composition shown below, using talc (Q' uniform grains) as the filler particles and casein as the stone agent.

Talc 100 heavy jI; part casein 2 1]tt tree
5oo //゛-For the support, competitive page paper was used as in Example 1, and this support was used. Recording 1. Dry painting of the composition 11 M
．． The recording material was coated by the blade-tar method at a temperature of 20 g/m' and 11 coats, and dried by a conventional method to obtain a recording material. Using the recording liquid, the recording characteristics were evaluated in the same manner as in Example 1, and the results are shown in Table 3.

Example 4 - The viscosity of the recording material used on the ground side 1 at 25°C was 3. Using a recording liquid with the following composition of Ocp, ζ-
Thermal energy L- is applied to the recording liquid in the recording head.
Then, to the on-demand type multi-function device that generates droplets and performs recording, l·(discharge orinus f 35-1 heating resistor resistance value 150Ω, drive voltage 30V, frequency 2KHz) is supplied to the recording device. Full-color f-4 reeds,
I recorded the throat.

Yellow ink (composition) C, 1, Ant Yellow 23 2 Double star partial oxidation, glycol 3Q //Water
7Q tt1 center ink (composition) C1, Ashit I Red 92 2 parts by weight Siylene glycol 30 tt water
7Q tt cyan ink (composition) C01, Tirect Blue 88 2 tunjlI8b
Diethylene glycol 301/water 7Q
ttThe recorded image obtained was clear and had a certain color tone, and the dots were good.

Comparative Example 1 Commercially available AR-I coated paper (product name: S
Evaluation of inkjet recording characteristics was carried out in the same manner as in Example 1, using K Coco-1 (manufactured by Yamakawa Kokusaku Pulp Co., Ltd.) and using the six types of recording liquids used in Example 1. The results are shown in Table 4. It should be noted that approximately 15% of the surface of the coating layer of this paper
A scanning electron micrograph at 00x magnification is shown in Figure 2.

Comparative Example 2 Commercially available non-coated paper No. 17 (product name: Ink Sheet Recording Paper M, :'E!!!?I! Paper Co., Ltd.) was used as the recording material, and the recording liquid was the same as that used in Example 1. Table 5 shows the results of evaluation of inkjet recording characteristics using six types in the same manner as in Example 1.

&-1 Table-2 Table-3 Table-4 Table-5

[Brief explanation of the drawing]

FIG. 1 is a scanning type photomicrograph of the surface of the recording layer of a typical recording material used in the present invention at a magnification of approximately 1500 times. Figure 2 shows +IIIk one line 1.
Paper surface + scanning electron microscope with the same magnification as l'Ii: A
It is. q, effect 1'1 output IX + - person Key Non Co., Ltd. Figure 1, etc. 238, ``Continuation IF, #; (Mrs.) % formula %) 1, 'l (DiI display Showa 5 Fi 1 Patent,) 1 Application No. 1133126-; 2. Name of the invention/I/Research 1. Recording power 7 people 3.
Relationship with person who does L / 1 list f1 Special 1:1 Applicant (100) - Ki Yanon Co., Ltd. 4th generation Jllj people + fi Tokyo 1 No. 16 Kowa Hill 8 Tumor-5, Amendment Order No. 11, 1982 1 Jl 2511 Dispatch 6, Supplement 11- Subject 7, Contents of the Supplement (1) Specification 11: Page 24, lines 2 to 5 "Fig.
r, Figure 1 shows the power of the present invention l), which is suitable for use in
◇
f - Existing arm 1' + [ to / - about 1500 by WJ imitation mirror (drawing substitute for 1) is true, 2nd
1] is a drawing-substituting photograph J' of the surface of a commercially available coated paper taken with a λ-scanning electron microscope. ” in the description.

Claims (1)

[Claims] 1. Inject a recording liquid into the hole B through the opening through the pores, and apply this recording liquid to the support to form a recording layer containing a filler material. Inquiry into the recording layer 4
In an ink jet recording method in which recording is carried out by recording, the recording material has a regular particle shape of the filling I on the surface of the recording layer, and the recording material The liquid must have an ice content of 1,111 yen within the range of 20 to 1,590 Tohoku%!II+ characteristic or ink Sony 21 Recording power 7 people.