JPS5954594A - 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 specific recording liquid 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 such as water and adjusted is applied onto a supporting substance to obtain 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. Meanwhile, a recording liquid, which is adjusted so that its surface tension at the temperature of 20 deg.C is within the limits of 30-60dyn/cm by adding thereto a surface tension adjusting agent such as a surfactant, is introduced into minute holes. Then, this recording liquid is made to stick, by an ink jet method, onto said material from an orifice communicating with said minute holes, and thereby a clear image is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method of inkjet recording, particularly multicolor inkjet recording.

Inknend Recording-V is a type of recording liquid injection method (e.g., electrostatic absorption force type, method of applying mechanical vibration or displacement to the recording liquid using a piezoelectric element, heating of the recording liquid). The recording liquid (
Generate small droplets of ink) and fly them,
・Part)'i し< is the part to be recorded on paper or other recording material 4-1
L is a type of recording that produces less noise and can perform high-speed printing and multicolor printing.
IE I-1.

Recording Ifk for ink side recording includes completeness,
A water-based material is used for -1 due to printability.
-F, the recording layer and 15 are either conventional paper or general 1.
．． '' has been used for -C recording using liquid ink.
:) In this case, it is generally a problem that printing is done with recording liquid or recording paper 1 so that the print does not become blurred, and also that the liquid dries out quickly after recording, which is disadvantageous.'' It is desirable not to contaminate I7.

7) In particular, in the multi-color ink side recording method using recording liquids of different colors as in Buddhist utensils 7, the following points are true: Even if there is, please make sure that the recording liquid that has been removed later does not mix with the recording liquid that arrived earlier, disturb the f-ink dots, or flow out. is recorded 11. Diffusion 1, 2, A〉
・Kudoso 1 1 yen or more than 1. not grow larger,
3) The shape of the river should be close to a perfect circle, and the riverside should be smooth.

4) R: Keto, 1. The e degree is high, 1.71. The surrounding area is blurred (no dirt, -), 5) The color of the recording material is white, ・Color with the ink l” ・Last 6) The color of the recording liquid or the recording material should not change, V) There should be little variation in the recording material (e.g. wrinkles, wrinkles) before and after recording; Is it necessary to stir all the costumes?V?

It is understood that in order to satisfy this requirement, it depends largely on the characteristics of the recording material and recording liquid used, but the current LI
! Currently, there is no way to find an ink-solid/1 recording method that meets the various demands of writing.

-t For example, considering the relationship between the surface tension of the recording material and the recording liquid [7], it is possible to record by using a recording material that is different from the conventional recording layer. Let's go,
On the surface of this recording layer, there is a small '' shown in Figure 2.
- Since there is no gap L2 (ti'+: L), if a recording liquid with a high surface tension is used, it is prevented from penetrating into the gap, and the absorption rate of the recording liquid becomes slow.

Therefore, if a recording liquid with low surface tension is used in order to increase the absorption speed 'cL] / Co-1, as in the case of using paper, the spread of the recording lfk in the direction of the paper's own blade will increase, resulting in good printing. The contradictory problem of not being able to obtain M was not resolved.

The purpose of the comparative invention is to solve all the problems that the prior art could not solve in the technical field No. 1-! There is one thing that makes me want to add it. Particularly, the present invention satisfies the following requirements in recording full-color images using a plurality of color recording liquids according to the ink side recording power type.

Another object of the present invention is to provide a novel inkjet recording method that can exhibit excellent recording properties over a wide range of recording liquid surface tensions.

Items 1, υ, and other 11 objectives are achieved by the present invention described above.

In other words, 5? :A recording liquid introduced into the pores is passed through the pores U, is sprayed from the opening 11, and the recording liquid is applied to the support 1-+a recording layer containing knee filler particles S. established (
1-(Naru recorded 4! Let's watch 11 times and record t-i)・
In the case of ink recording, -C1 A record of the surface number of the recording layer of the small regular shape of the recording material or the filling and collapsing material. Heat the recording liquid to 20°C (t;
It shall be within the range of ノ'(': 60 dyn/co).
He has a two-one, one-one record at f7', which is characterized by '↓'I.

The recording material used in Comparative Inventive Power Bank Koi-C consists of a joystick and a recording layer provided on the surface thereof.

Is it appropriate to use paper as a support for the recording material?
′! Is it cloth, porous + T1 wood, porous 7It materials such as wood, resin, etc.? Many materials can be used, such as genus, corvus, etc., and the choice of which one to use depends on the record and application.

The recording layer is finally composed of filling 4A particles and a stone agent.
, C is the example λ is the warping force, rishi-, talc, keso I-
2.) 5 acid 73 Rujiu I., Kinuta acid cal...Nuj.
, barium sulfate, 100% oxide, -++i lead oxide, zabu, white f1.

11. White inorganic pigments such as Sui・Bo/, Aluminum, Seo・Di・・・ etc.: Boris J Ren, Poly 1,000 Shin, Original Polmarine resin, Polytetrachloride, Volimel L methacrylate 1,69 Organic polymer-
Zero (f1' or raise μ, this l':) (7) 1 Insert l or lg).

In order for the surface of the recording layer to appear as if porous + '1 inorganic face *1 condyle - r amorphous J[: shape or #le are scattered, the porous P1 inorganic face book I used is Grain A or 1 to total 30μ
Inertia, more like Ilf or 3 convex metal 201 blood f11 degree t)
It is ep or I7. If the grains of the porous f1 inorganic face book (t't) are too large, it will cause ink to fall.
1P1 is damaged and the resolution of the recorded image is low, which is not good.

In addition, the filler particles added to the recording layer are dye-absorbing 7It.
It is preferable that the material with a high l (l f-! L <, further i, - has a porous structure. This is because the force trapped in the surface layer of the recording layer gives a good coloring property.

Other power 5. As a nucleating agent, starch, gelatin, b-zein, Aphyago 15, alkyne anti-sorghum, carboxymethyl cellulose 1-, cyenyl pyrrolidone, polyacrylic chu-sorta, polyacrylamide-based water-soluble polymer, Synthetic wood 11fi latte such as synthetic goimuradenx, couscous, polyhinyl vular, polyhinyl ryolite, polyhinyl acetate, polyacrylonitrile, polymer f-j
Ls methacrylate polyhinyl formal, melamine resin, polyamide, fusil resin, polyj
There are 91 solvent-soluble resins such as Fushitan and algint resins, and only one of these is used.

In addition, the recording layer contains a dispersant, a fluorescent dye IIPH adjustment layer,
Various additives such as antifoaming agents, lubricants, preservatives, and surfactants can also be mixed.

The recording material suitable for use in the present invention is prepared by separating various components of the recording layer in a medium such as water.
B, doper J-de 1 'metsu dai, sp [7-2] - ting υ, , air knife coach, f ng θ, etc. support 1.
+f body 1-, and then Ijf and dζ dried quickly to make 1.The filler material 1'- of the coating I and the 11 of the joint 1. cut are used as a ticket. Banko filler grain 1'
i00 ton (#￥ r: for R., -C binder ka 10: '1; 100 ton;,) some Ie! In this case, when the average particle size of the filler particles is large, it is best to use as few stones as possible. The weight of the recording layer on the support is usually 1 to 50 g/'m
’ degree (dry coating - 4)) on the support 1.
do. In addition, fmashi5〈 is about 2 to 30 g/m' (
It's good to have 4 pieces (1 state).

FIG. 1 shows approximately 1,500 layers 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 true, and its unique human blood condition is well minimized.In other words, the relatively large, irregularly shaped filler R with a diameter on the order of zero is the main component of the recording layer.
The particles appear on the surface of the recording layer when they are placed randomly, and between these particles there are many large voids that function as ink absorption holes, so to speak, debris of various sizes is formed. It has an irregular surface structure that cannot be described as scattered. Of course, these surface numbers, - pulled filling machining ◇ r too &'
It is fixed within the recording layer by the agent and does not easily separate from the recording layer.

The power θ of the present invention, the records used in the report 7 & i, dyeing II
It consists of a recording agent such as and a liquid medium component. Generally, when recording at 4i using a recording liquid, it is important to measure the relationship between the recording material and the physical properties of the recording liquid. ! +'
A recording liquid with good flexibility to the recording material is used as I.
There are spirits that choose to use. That is, the critical table 1I'IJ tension of the pre-treated recording material is 40-50 dyn/cm.
Therefore, it is preferable to use a recording liquid having a surface tension close to the value of . The recording liquid used in the method of the present invention has a temperature of 30-6 at 20'C.

dyn/cm, Qf preferably 35-55 dyn/
cm, particularly preferably in the range from 40 to 50 dyn/cm. When printing using a recording liquid with a surface tension lower than this range,
Is the wettability to the recording material good?The spread of the printed I/T becomes thick. = force, + ii'' surface tension, -:
When a recording liquid with a high surface tension is used, the wettability of the recording material to the recording material becomes poor, and as a result, ink absorption and dot density are likely to be low.

The liquid medium components of the liquid #i used in the method of the present invention include not only water alone within the range satisfying the surface tension of record 7 (★), but also water and various water-soluble components as desired. ] Used in mixtures with organic solvents, etc.

-l As a water-soluble 45-organic solvent, for example, methyl! “
le・1−le, I chill/le”−le,
sopropyl/ru'-ru, n-j thyl alcohol, 5eC-/nal'-ru, tert-notyl alcohol. Alkyl alkyl groups having a carbon atom r number of 1 to 4, such as -f-Sonote alcohol, etc.; I-Nme is a ketone alcohol; detrahydride [U7N, dioxane, etc.]-
- Chills; poly/lugylene glycols such as polypropylene glycol, polypropylene glycol, etc.;
6-hegisant 1-9, -f 1-9, -kryl, hexylene 1-l, die 4 lengriny]-l't
Alkylene' group of 2 to 6ov (7) Irugile 7 glycols containing carbon atom 1', Glytosu', Tchi1
/nr! Ricoh) Remeyl ether, p, ・]-thire ′,′ly]-l methyl (or 1,000 ru) 1-ter, tos L 1,000, 1,000,000,000 Examples include -7-rug 9 polyvalent alni l -, 1 lower alkyl + 1/ether lamp 1, etc.

Among these many water-soluble 11 solvents, polyhydric alcohols such as sienna, glycol, trichol, ibricol, (or ingenious) ether, etc. Lower furkyl ethers of alcohol are to'!
It's something new. Polyhydric alcohols emit water in the recording liquid and precipitate out of the recording agent. A wetting agent for preventing the clumping phenomenon (1) is preferable for 4-C and 1I' because the effect of 7-C is 11 greater.

In order to adjust the surface tension of a recording liquid containing such liquid medium components within the above range, various types of cationic, anionic or nonionic liquid medium components are used. [Add agent, T-tanolamine, tri-1-27-L-imine' to adjust surface tension/ill, -7L-can be added.

It is also possible to add a 1.1Ni+J solubilizer to the recording liquid.A typical 11-1itsill is a N-containing heterocyclic geton, and its [1] action is The solution 111 for the liquid medium of
2-imitalycinone is most frequently used.

A recording liquid prepared from such components has excellent recording properties by itself. The subsequent discharge chamber crab t'L), stability (f stability, 61) (excellent fixation to recording material), but in order to leave these characteristics +1 behind, further process additives were added. For example, viscosity modifiers such as polyhinyl alcohols, celluloses, water-soluble resins, and PR modifiers depending on the buffer solution may be used.

In addition, in order to prepare the recording liquid used for the type of ink that uses a recording liquid, the following ingredients are required: salt IL, ammonium 11, sodium chloride An inorganic type 11.1 type resistivity adjuster is added.When applied to an ink agent force type that ejects recording liquid by the action of thermal energy, thermal physical property values (e.g. , specific heat, heat 111, tensile coefficient 1,8υ
, conductors, etc.) may be adjusted.

According to the uninvented method, even if a different color recording liquid has been deposited in several places over a short period of time, there will be no phenomenon of the recording liquid flowing out or spilling out, and high resolution 1 can be achieved. (1) An image with improved color development can be obtained. ]7 Even if you use a recording liquid with a wide range of surface tension depending on the recording liquid output type, recording purpose, etc., these crushed special +J[(
It is excellent as an inkjet recorder when performing pull-color recording.

Hereinafter, according to the examples, the uninvented method will be further described in 1. -T Explain in detail.

Example 1 Silica and Busyl E150 as filler particles. Product name, 1
Manufactured by Ippon Shiri Kotogyo Co., Ltd., I. Hitoshi IQ, fi-gi, 5
11111) and polyvinyl/lunyl and SBR Σ7 as binding agents, a composition for coating I was prepared based on the phase composition of 1.L7.

Silica Explosion 0 ΦF,
5 //Wednesday
500 tt-・C is Jlε; size power 35 seconds based on P8122 (
7)-IIQ High quality paper (jf M, f: E' 5 g
/m') and coat this support 3
III Dry coating of M1 product a 15 g/'''
m' + 7) ratio -]-tar method Shiko 5Y coating 1 and dried by the Tofu method to obtain a recording material.

Figure 1 shows a scanning micrograph of about 1500 nm on the surface of the coating layer of the obtained recording agent.

For this recording medium, use one type of ink for on-temant type inkjet recording, which uses one type of ink to eject recording liquid 1.1 times by pien vibration. 1 certain 50μ, piezo vibration f drive voltage 8
[]V, frequency 4KHz) using the recording 'A' position.
, then input/7th:r-ent record, record')N evaluation: l"j'-)!=.

・Ink No. A: Surface tension is approximately 60 dyn/cm
(Ail composition) Kojiren Griny 1-L 3o
Heavy x some water
7 Q ttC, l, evening (k,
·evening!・-Sol-862tt ink No. B: Front + n
j z force is about 55 dyn/cm (composition) edge, 1-3 o heavy early part water
7 o.

Ayatinol EhI (lo% water) 0.05 tt
(Kai u'+i activator, Yoken) - manufactured by γ-In Chemical γF)
C, 1, Ri(1/Rido Blue 86 2 // Ink No. C: Surface tension is approximately 50 dyn/cm (Composition) Echishi Nkuconokol "OmEtiM"
Water 7Q
ttr f,y -Jl/E H (10% water)
0.07//C, 1, Daishi Rido Blue 86
2 tr ink No. 0: Surface tension approximately 45
dyn/em (Composition) Nib-Langericol
30 parts by weight lf, 7 Q tt Ar[chinol El ((10% bottle) 0.5
//C, 1, evening 4 1y ノ1 h j
Le --867tt ink No. E Surface tension is approximately 40 dyn/cm (Composition) Diethylene glycol
3 Q m, S, 'j 8R water
7o 7゜Acebuonol EH (10% water) 1.1//C, 1, Gu (Lech Blue 86 2 //E7'Yu No.
F: Surface tension is approximately 35 dyn/cm (Composition) Propylene'Griny]-rumonomethyl 1-pool 30 Ichiyabeki
7Q tt
7Se1-Nol EH (10% water) 1.1)//1;I
. Tyref (Blue SE 2 TT ink No., G: Surface tension is approximately 30 dyn/cl!L (composition) Propylene glycol monomethyl needle 50 Φ4141% water
5Q tt Acedinol Ell (10% water) 0.1//C, J, Dairefj True 88 2//Table 1 shows the evaluation results of the recording properties of the recording material.

The valley evaluation, lI'i it, in Table 1 was measured according to the following method.

1) L',, To density, print don't Sakura Micro ≠
The measurement was performed using M-5 (manufactured by Konishi Rokugyo Co., Ltd.).

2) 1.7) The ttz shape was determined by observing the printed image with a stereomicroscope, and marking a round shape was marked Δ if it was 01 round or slightly distorted, and × was marked if it was a small regular shape.

3) The degree of bleeding is determined by measuring the diameter of the printed material using a microscopic microscope.

a l) Color! Then, the Y condition is to compare the brightness and brightness of the colors of the inkjet recorded images by illumination, and the best one is C), the lowest one is X, and Olo, l-\, ×
It was divided into two parts.

5) 1 for ink absorption is 3 F for 1 second after overprinting, there is only ink flowing out from the surface of the recording material, and the bright # of the image is 0, otherwise Let × be I
child .

Example 2 Calcium carbonate (average particle size: 3 scales) was used as the filler, and -cr starch and 5BR3 textures were used as binding agents. A composition was prepared.

Calcium carbonate 100 tons: Jj part temp-3Q tt SBR nra/cus 101/ water 300
tt-force, the support was the same as in Example 1-fi
+, using paper, this support 1: i, yam,: , d
2 coats 1- Dry coat the big fish f-,'Jj20g
In the old 11th match of /m', there were 7 players in play (, -
YoiJ Nuri [Jin 2, Jō 7), by Kenzai,'! A recording material was obtained.

Table 2 shows the results of evaluating this recording material in the same manner as in Example 1.

Example 3 A coating composition having the following M1 composition was prepared using talc (.1, uniform particles 1 (17 tiles)) as filler particles and caseinta as a binder.

Kuruk 100 medium, Mt RR casein 20/l water 500
/1-Force, support and [7] Example 1 and general 1-textured paper, dry the composition for coating on this support 12 [,', N 20 -i0 of g/m'
h Tape 1; By coater method (1 coat T17, dry in a base shape to finish recording material. Apply this recording material once as in Example 1.1'l1ll L Ta')
: ヲTable 3 +: Small T.

, (Male side 4', (For the recording material used on male side 1, use a recording liquid with the same composition as the surface tension at 20°C or 54 dyn/cm [7, These recording liquids are used for recording 7 F An on-board printer that generates droplets by applying heat and L energy to the recording liquid inside.
77 type multi-hand (11, + output orifice diameter 5JIIn, heating resistor resistance 150Ω, drive'
A full-length ink-and-end recording was performed by supplying a pressure of 30 V and a frequency of 2 KHz to a recording device.

Ye0-ink (composition) C,! , Assin toy 10-23 2 Claw φ part edge
'Glycol 3011 water
70/l-・zentaisoku (
composition) (: , l, a, 1゛shi, tsu
l'92 2 Qγ
et al', FIB Siechi[//Glicono t,
30 //Wed
7Q tr cyan ink (Ml composition) C1, evening [7・rid blue sea 1 nalen glycol:] O tt tree
7Q
//IIII:) The recorded image is bright with a predetermined color tone, has a flat shape, and has good ivy absorption.

Comparative Example 1 As the recording material, 1C city water 7-1 paper (trade name: SK Co. 1, 11. - Ink sheet, 1. Recording characteristics. Example 1. ! −
Just like last time, there are 11. The results are shown in Table 4. Note that the q-axis of the traversal electron microscope, which is approximately 1500 times larger than the surface of the limb covering layer of this paper, was as shown in Figure 2.

Table-1 Table-2 Table-3 Table-4 4, Figure + (+1) O'a 'F, t Theory 1! It first
The figure shows 12 suitable for use in 7shi) η Light Force II.
A scanning telephoto microscope' (g) at a magnification of approximately 1500 times the surface of the recording layer of the record storage.
This is a J-scan type '1 series r-microscopic photograph of the surface of the paper fft 44. (Method) Display of % formula % 1, 1>f't Showa 5 Fi 1 Special,; 1 Application No. 163127? Name of 0 starting 11, I~, Kushiendo recording method 3, Supplement II- name, )) Matter 1 ■) Special + j'l applicant (100)
Canon Co., Ltd. 4th generation Director Address: 16th Kowa Hill J 3rd floor, 16th Kowa Hill J-II 9th 20th Street, Minato-ku, Tokyo (Minato-ku, Red Handling I J-II) Name: 7021 Hayashi H, 1
4. Top (585N882 5, ?li tl-instruction's 11th call III'+ II+ 58i 11.J'l 25 Li
[Drawings] of the subject specification of Supplement 6 L1-; 11 Simple explanation [9j] column.

7. Contents of amendment (1) Specification, page 23, No. 2~! '5 line [Figure 1 is...lr, , : page]. 1 Figure 1 shows the surface of the recording layer of the recording material suitable for use in the method of the present invention. 1500 fi"; and Figure 2 is a photograph of the surface of Sansui's Niko-1 paper (344 scanning type 'Tun I' microscope). Revise 11.

Claims (1)

[Claims] 1. When the recording liquid introduced into the a hole is passed through the pore 1.
Inject from -1 and 7. This recording liquid is used as a support 1.13 as a filler material and 7. An inkjet recording property number for recording with a recording material having a recording layer containing f-, in which the +iiij recording material has small regular particles of the filler. The shape of the recording layer is expressed on the surface of the recording layer, and 1- The ink sheet/1 recording power is ν.