JPS5930875A - Ink composition for ink jet recording - Google Patents

Abstract

PURPOSE:To provide titled composition of rapid dryability, capable of affording high-quality records, also having excellent delivery characteristics through nozzle, comprising a water-soluble dye, a surfactant having, as the hydrophilic group, a polyoxy-hydroxypropoxy group, and water. CONSTITUTION:The objective composition comprising (A) pref. 0.5-7pts.wt. of a water-soluble dye such as direct, basic, acid, reactive dye (B) pref. 0.5-15 pts.wt. of a surfactant having as the hydrophilic group, polyoxy-hydroxypropoxy group, and (C) water. Said surfactant is pref. a compound of formula I or II (R1 is butyl, amyl, octyl, nonyl, or dodecyl; R2 is H, methyl, amyl, octyl, or nonyl; R is aryl, octyl, nonyl, dodecyl, or octadecyl; X is O or S; n is 1-10).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an inkjet recording ink composition, and in particular an inkjet recording ink composition suitable for an inkjet recording method in which ink is ejected by pushing out ink from a nozzle due to a rapid decrease in the internal volume of an ink chamber. It is related to.

Conventionally, the inkjet recording method records information without bringing the recording head into contact with the recording carrier by controlling and ejecting ink onto the recording carrier. Due to its ability to record data, etc., it has been adopted in terminal printers, etc., and has become rapidly popular in recent years.

Conventionally known inkjet recording methods include a rapid reduction in the internal volume of a container, an inkjet method that ejects by extrusion or suction with a constant pressure, or a signal voltage between a nozzle and a counter electrode. An inkjet method is known in which ink is electrostatically accelerated and ejected from a nozzle by applying a current, and an ink mist method is known in which a mist is generated by vibration of ultrasonic waves.

This type of inkjet recording ink includes (1)
8. Do not place it on the recording head nozzle and cause clogging.

(2) It must have appropriate physical property values to satisfy injection characteristics (ejection stability, frequency response, etc.).

(3) Do not corrode materials that come into contact with the ink. and (4) it is required to be stable for long-term storage. Further, when the ink is used for printing on a recording medium, the following characteristics are required: (5) It should be quick drying.

(6) Good printing quality.

(7) Good preservation as a recorded image. (light resistance, daffodil resistance, etc.) etc. are required.

Among the above characteristics, for example, under the condition that the ink is difficult to dry as shown in requirement (1), the ink must dry quickly when printed on recording paper, as shown in K f5+. Therefore, (1) to (7)
) It is very difficult to produce an inkjet recording ink that completely satisfies the requirements of (11-(
In many cases, progress was made in the direction of satisfying requirement 7). For example, requirements (1) and (5) above can be met if the device is equipped with a drying device to speed up the drying of printed matter, or if ink-absorbing paper is used as the recording paper! - I can do it.

However, the use of a drying device increases the size of the recording device, is energy-efficient, and requires the use of a predetermined type of recording paper.

On the other hand, although various improvements have been made to inkjet recording inks, the above-mentioned IJI~(7
) has not yet been found that satisfies all of the requirements. For example, it has been proposed to use oil-based ink in order to satisfy the quick-drying property described in (5) above, but although this oil-based ink certainly satisfies the quick-drying property, it has poor ejection characteristics from the nozzle. Bad (, Print quality is still unsatisfactory (, Not practical).

In other words, (2) and (6) above are no longer satisfied. Furthermore, as proposed in JP-A-56-57862 VC, an inkjet recording ink that attempts to satisfy the quick drying property of (5) above is proposed by dissolving the components of the paper. This type of ink has an adverse effect such as dissolving the material of the ink contacting part of the device, and does not satisfy the above (3), and also the above (5) and (6) are insufficient and are not practical.

Another way to achieve even faster drying is to use dyes, wetting agents,
An inkjet recording ink consisting of a surfactant and water has been proposed. However, although the conventional combination of wetting agents and surfactants may have little negative impact on other requirements, the quick drying properties (5) and the printing quality (6) are not sufficient. This is the current situation.

In other words, ink having only intermediate permeability not only does not satisfy quick drying properties, but also has the problem of extremely poor printing quality.

As a result of studies, the present inventors have found an inkjet recording ink that satisfies both quick-drying properties and print quality by imparting sufficient permeability to the ink and can withstand practical use, thereby completing the present invention.

An object of the present invention is to provide an ink composition for inkjet recording that has an excellent drying speed on recording paper.

Another object of the present invention is to provide an ink composition for inkjet recording with excellent print quality.

Another object of the present invention is to provide an ink composition for inkjet recording that has excellent jetting characteristics from a nozzle.

Still another object of the present invention is to provide an inkjet recording method that can be suitably used with the ink composition for inkjet recording.

The ink composition for inkjet recording (hereinafter referred to as the ink of the present invention) is characterized by containing a water-soluble dye, a surfactant having a polyoxy-hydroxypropoxy group as a hydrophilic group, and water. ) to be achieved.

In particular, the effect is enhanced by using a surfactant represented by the general formula (1) or (■).

Island CH ■ In the above general formula, R1 is an alkyl group (e.g., butyl group, amyl group, octyl group, nonyl group, dodecyl group), and R7 is a hydrogen atom or an alkyl group (e.g., methyl group, amyl group, octyl group, silicon represents an aryl group or an alkyl group (eg, evaoctyl, nonyl group, dotecyl group, octadecyl group), X represents an oxygen atom or a sulfur atom, and n represents a positive integer from 1 to 1o.

Said Jt.

The alkyl groups in R1 and RK may be linear or branched, and may be primary, secondary, or tertiary alkyl groups.

In the above R,, rt, and R, the alkyl group for R4 has 4 to 12 carbon atoms, the alkyl group for R2 has 1 to 12 carbon atoms, and the general alkyl group has 1 to 12 carbon atoms. 8 to 22 are preferred.

Typical specific examples of compounds represented by the general formulas [■] and [formula] are listed below.

(1) n=]~3 n = 3~7 n = 3~7 n=4-8 C1(.

(10) CH NawateC8H,, -0(-CH,Cl-1c)-1,0-)-
11(12) CH C,l! I-1,7-0(-Cl-1,CHCH,O-
)-H(13) 1-1 C,H,,-S +CH,CHCH20SH(14) 1-1 C,,R2,-S (-C1-12CHC)1.0-)
-H (15) CH C,, R3, -8 (-CH□ClICH2O-) -H Synthesis example-1 (synthesis of compound example (1)) p, which shows representative synthesis methods for these compounds below. -tert-7mi) L' 7 x no, 82g (0.5mol)
Add 1.511 of sodium diluted to 135 to 1
The mixture was heated to 40''C, and 37 g of glymidol was added dropwise over 3 hours. After the reaction, the temperature was lowered, benzene was added, and after neutralization with hydrochloric acid, the benzene was distilled off to obtain the desired product.

Synthesis Example-2 (Synthesis of Compound Example (3)) P-nonylpheno-, llz 55g (0.25mol
) to 135-1 by adding 0.75g of sodium hydroxide.
Heat to 40℃ and first add 18.5g of glycidol (0,
25 moi was added dropwise over 30 minutes, and stirring was continued for 15 minutes. Furthermore, Glycidor 37! i' (0.5m
ol) was added dropwise over a period of 1 hour, and the reaction was continued for 1 hour.

After cooling, it was neutralized with 0.75% acetic acid to obtain the desired product.

Synthesis Example-3 (Synthesis of Compound Example (5)) 35.1 g of 24-di-tert-aminophenol (
Add 0.4 g of IJium (hydroxide to 0.15 mol) and add glycidol 11.19 g while stirring at 130°C.
(0.15 mol) was added dropwise over 20 minutes.

After stirring for 15 minutes, glycidol 44.4
g (0.6 mo, g) was added dropwise over a period of 1 hour and 45 minutes.
Stirring was continued for an additional hour. After cooling, the mixture was neutralized with 0.4 g of acetic acid to obtain a brown transparent viscous target product.

The surfactant according to the invention having a polyoxy-hydroxypropoxy group as a hydrophilic group provides an ink with sufficient permeability, resulting in an ink that dries quickly and makes it possible to record high print quality.

The amount added is preferably 0.5 to 15 parts by weight based on the total amount of the ink. Furthermore, since this surfactant also acts as a solubilizer for water-soluble dyes, stable ink can be obtained without precipitation of dyes even during long-term storage.

The surfactant containing polyoxy-hydroxypropoxy as a hydrophilic property according to the present invention is not only effective for quick drying (but also has a wetting effect. Therefore, it is not necessary to add a new wetting agent). Although it is possible to satisfy the performance as an ink, in the present invention, adding a wetting agent further gives more preferable results.

Wetting agents used in the present invention include aliphatic polyhydric alcohols, alkyl ethers of aliphatic polyhydric alcohols,
N-alkanolamines, N-hydroxyalkyl-
Examples include 2-pyrrolidones, N-vinyl-2-pyrrolidone oligomers, and N-hydroxyalkylformamides.

Particularly preferred wetting agents have a high paper penetration rate, ie, the volume of liquid that can penetrate per unit volume of paper.

The penetration rate of the wetting agent into the paper is determined by dropping a certain amount of the wetting agent onto paper of known thickness and measuring the spread area.

The wetting agent according to the present invention preferably has a penetration rate of 30% or more, particularly preferably 40% or more.

Preferred wetting agents are ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,5-bentanediol thiodiethanol,
Propylene glycol, polyethylene glycol jetanolamine, N-hydroxyethyl-2-pyrrolidone, α-pyrrolidone, dimethyl sulfoxide, etc.
Particularly preferred wetting agents are ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, propylene glycol, polyethylene glycol, jetanolamine α-pyrrolithone,
Dimethyl sulfoxide.

In conventional water-based ink for inkjet recording,
Generally, as the age of the wetting agent increases, both quick drying properties and print quality deteriorate. However, in the ink of the present invention, surprisingly, more favorable results can be obtained when a certain amount of wetting agent is added. However, when the amount of wetting agent added exceeds 90 cents by weight, Since the viscosity increases, the wetting agent is preferably 90% by weight or less, particularly preferably 80% by weight. Two or more types of wetting agents may be used in combination.

Water-soluble dyes used in the present invention include direct dyes, basic dyes, reactive dyes and acid dyes.

The amount of these dyes added to the ink of the present invention is determined by the color intensity of the image printed on the surface of the printing medium.

The color intensity of the image is determined by the interaction between the ink and the printing medium, and the amount of these dyes added to the ink should be determined in relation to the printing medium. For the preparation of cyan and black inks, it is preferable to add one or more water-soluble dyes to each color ink in an amount of 0.2 to 15 parts by weight based on the total weight of the ink composition, and preferably 8 to 15 parts by weight based on the total weight of the ink composition. It is desirable that 0.5 to 7f<-m1 part.

Examples of direct dyes, basic dyes, reactive dyes and acidic dyes that can be used in the present invention include the following dyes in addition to the dyes disclosed in JP-A-49-89534.

CI) Direct dye C, I, Direct Ye eyes OW 27 (C
,I, 13950)C,I,I]rect Y
yellow 28 (C,I, 19555)C,
I, Direct Yellow 33 (C, I,
29020) C, I, Direct Yell
ow 39C1i, I]rect Yellow
58C, I, Direct Yellow g
6C, I, Direct Yellow 100
C, i, Direct Red 6375 (
C, I, 25380) 79 (C, I, 29065) so (C, I, 35780) 83 (C, I, 29225 C, I, Direct Red 99r
# 220 1224 # # 47 (C, I, 25410) g
t 48 (C, I, 29125)
# # 51 (C, I, 27905)〃
90 I # 94 C, J, Direct Blue 1 (C,
I, 244H1) # 8 # 71 (C, I, 34140) #
76 (C, I, 24411) # 78
(C, I, 34200)〃80 #86 (C, I, 74180)〃90 〃 106. (C, I, 51300) #1
08(C,I, 51320)I 123 (
C, I, 26705 ># I 163
(C”, I, 3356 (1) C4, Direct
Blue 165# Black 19
(C, r, 35255) f 32 (C, L
35440) # 38 (C, I, 302
35) #71 (C, I, 25040)
# 74 (C, r, 34180) #
75 (C, I, 35870)〃 112 117 CII) Acidic dye C, I, Ac1d Yellow 17 (c, t
, 18965 ) 9 25 (C,I, 18835n29 (C,I, 18900) 38 (C,L 25135 ) 9 9 1 2 C,I, Ac1d Red 1 (C,I,
18050) C, T, Ac1d Red
8 (C, (, 14900) 1 # #
32 (C, I, 17(+65)#
rr y 37 (C, I, 17070)
# # # 42 (C, I, 1
7170) # tt s 57
1#' 115 (C, I, 2720 (1
) # # # 119 #
y s 137 # # l
133 (C, I, 17995 n# /
'# 134 (C, I, 2481 (
1), # #154 (C,L
24800) * s p 186
(C-1, 1881 (n) u l' /J
249 (C, I, 18134), #
#254, # #
256C,I, Ac1d Violet 11
(C, 1, 17 (160) 34 (C, I, 61
71(1,6180(])5 tr z Blue 29 (C,
I, 20460) 26 c, r, Ac1d Blue 171# 1
75 # 183 C, I, Ac1d Black 1 (C, I
, 20470) #24 (C, I, 26370) s 26 (C, I, 27070) y
48 (C, l, 65005)〃 52
(C, T, 15711) 〃58 〃60 # 107 〃 109 〃 119 # tt p 131p
z I 155 (IIIJ reactive dye-
Fee C, I, Reactive L-+1ue 7 (
C, I, 74460) #14 15 #18 C, I, Reactive l31ue21 25 C, I, Reactive Yellow 1#
2 (C, I, xsq7z)' 3
(C, I, 13245) #13 〃14 〃15 # 17 (C, I, 18852) C, I, R
active Red 26 (C, l,
17965) 〃 1] 〃23 〃36 C, I, Iteactive Violet 2
(C, I, 181571)〃 4 〃 8 9 [Closed Basic dye C, I, Ba5ic Yellow Moon (C,, I, 4
8055) C, I, Ba5ic Yellow
14#21 #32 C,I Ba5ic R,ed 1 (C
,I, 4516(1)〃2 (C,I, 50240
) N 9 (C, I, 42500) tL 1
2 (C, I, 48070) N 13 (C,
I, 48015) C, I, Ba5ic~'1olet
3 (C, I, 42555) 7 (C,
I, 48020) #14 (C, I, 42510) C, r, B
a5ic Blue 3 (C, r, 510
05 ) 9 (C, I, 52015 ) # 24 (C, I, 52030 ) I 2
5 (C, I, 52025) Other dyes that can be used in the ink of the present invention include chelate dyes and so-called silver z (1 white method photosensitive dyes (for example, Cibachrome manufactured by Ciba and Geigy)). Roazo dyes may be mentioned.

Regarding chelate dyes, for example, British Patent No. 1,077;
You can refer to the distribution of No. 484 Akira #181 yen.

Regarding azo dyes for photosensitive materials using the Kushi dye labeling method, for example, British Patent No. 1,039,458, British Patent No. 1.0 (14,95
No. 7, same; No. 1,077.628, U.S. Patent No. 2,
The description in the specification of No. 612.448 can be referred to.

Other additives used according to the ink of the present invention include, for example, when long-term storage is expected, to prevent or reduce the growth of bacteria and mold in the ink. You can add preservatives and anti-mold agents to it. A variety of preservatives are known to be useful for this purpose, and a desirable one is, for example, a 1,3,5-hexano-hydrotriazine derivative (Batilard 35; available from Hoechst).

In addition, a surfactant other than the polyoxy/hydroxy group-containing surfactant according to the present invention can be added in order to suitably adjust the surface tension that governs the wetting of the ink of the present invention on recording paper.

The surfactant is not particularly limited as long as it has extremely low solubility or interacts with the dye.

In addition, various inorganic or organic pHMs are used to prevent the pH of the ink from changing mainly due to absorption of carbon dioxide gas in the air during storage in the container or residence in the nozzle. Shocking agents can be added. Desirable pf (Buffering agents include, for example, carbonates such as sodium carbonate and potassium carbonate, but the appropriate amount for practical use is 0.1 to 5% by weight based on the total amount of the ink of the present invention. Preferably, 0.1 to 2 weight percent is appropriate.

Furthermore, various chelating agents can be added for the purpose of masking metals and metal ions in the inks of the present invention. Typical examples include sodium gluconate, ethylenediaminetetraacetic acid (EDTA), disodium salt, trisodium salt, sodium salt of EDTA, and sodium salt of diethylenetriaminopentaacetic acid. For practical purposes, it is appropriate to use 0.1 to 5 percent by weight, preferably 0.1 to 2 percent by weight, based on the total kK of the ink.

The present invention can be applied to any viscosity and surface tension, but preferably the viscosity (25°) is 4.0 to 20. Ocps, surface tension (25°O) 20 to 50 dyn/m is suitable.

Example-1 Composition Weight %
After mixing the above components and stirring at room temperature for 3 hours,
A sample-1 of the present invention was obtained by using a membrane filter (TM-1) with a pore size of . Sample-1 was kept at room temperature (25
℃), viscosity 47 cps, surface tension 27.5 dyn
/crrL and ivy.

U.S. Patent No. 4. Sample-1 was adjusted to the parameters shown in Table-1. ] When the inkjet recording device described in Figures 1 to 3 of Specification No. 89,734 was filled with the inkjet recording device and inkjet recording was performed on plain paper, a clear yellow record with good print quality was obtained.

The drying time of the ink on the recording paper was 1 second or less, indicating good quick drying properties.

Table-1 Example-2 Composition Weight % The above components were mixed and prepared in the same manner as in Example-1 to obtain Sample-2 of the present invention. Sample-2 has a viscosity of 8 at room temperature (25°C).
．． Qcps, surface tension 28.4 dyn 70 m. When Sample 2 was recorded on plain paper in the same manner as in Example 1, a recording with a clear agenta color and good print quality was obtained. The drying time of the ink on the recording paper was 1 second or less.

Example-3 Composition Weight % The above components were mixed and prepared in the same manner as in Example-1 to obtain Sample-3 of the present invention. Sample-3 has a viscosity of 4.8 cps and a surface tension of 27.6 den at normal m (25υ).
It was /an. When sample 3 was recorded on plain paper in the same manner as in Example 1, a record with clear blue color and good print quality was obtained. The drying time of the ink on the recording paper was 1 second or less.

Example 4 Composition Weight % The above components were mixed and prepared in the same manner as in Example 1 to obtain Sample 4 of the present invention. Sample-4 has a viscosity of 6.8 cps and a surface tension of 27. It was dyn/σ. When Sample-4 was recorded on plain paper in the same manner as Example-1,
A record of good print quality was obtained.

The drying speed of the ink on the recording paper was 1 second or less.

Comparative Example-1 Composition Weight% The above components were mixed and prepared in the same manner as in Example-1 to prepare Comparative Sample-1.
I got it. At room temperature (25°C), viscosity is 6.8cp
The sS surface tension was 29.4 dyn/solder. The printing quality of the ink of Comparative Sample-1 was poor in that the recorded characters had noticeable feathering, and the drying properties were also poor.

Comparative Example-2 Composition Weight % The above components were mixed and prepared in the same manner as in Example-1 to obtain Comparative Sample-2. At room temperature (25℃), the viscosity is 1.8
cps, surface tension Itt 62.5 dyn 7cm
Y: Atta.

This Comparative Sample-2 had poor drying properties and poor printing quality as well as Comparative Sample-1.

Comparative Example 3 Composition Weight % The above components were mixed and prepared in the same manner as in Example 1 to obtain Comparative Sample 3. At room temperature (25°0), viscosity is 27.1cp
s, and the surface tension was 30.2 dyn 7 cm.

This comparative sample was the same as that described in JP-A No. 55-65270 (1988), but had poor drying properties, but the dots had a large diameter (too much) and the print quality was poor.

Example = 5 When the injection characteristics of Samples 1 to 4 and Comparative Samples 1 to 3 were investigated by changing the frequency of injection using the device shown in Example 1, it was found that all samples except Comparative Sample 3 had good characteristics. It's also worth it.

Also, after a week of leaving it indoors with the ink filled,
When I restarted the recording, comparison samples 2 and 3 were no longer compatible, but samples 1 to 3 remained in their initial state (
, good recording was possible.

Agent Yoshi Kuwahara Beautiful procedural amendment 1980 9) ] 12 L + Patent J1 Chief 11 + ' Kazuo Wakasugi 1 Middle Fl's Manpower ll + 'i 1980 Patent Fl'll'l No. 141
281 No. 2 Name of the invention Ink composition for inkjet recording; 3. Relationship with Sleeve 11 J°1 [A'1 Patent No. 8'1 Applicant's address Nishi-Shinjuku I J' l: 126, Shinjuku-ku, Tokyo Number 2 Name (
+27) Roku Konishi Photos - J17 Co., Ltd. Ii Nobuhiko Notification Office 11 Nobukasakuricho, Tokyo Column 7 of Detailed Description j, Contents of Amendment (1) The detailed description of the invention is amended as follows.

Specification page 17, lines 1 to 9 "C, I I Direct Blue 165'
N Blaek 19 (C-1s 3525
5) # # # 32 (C, I, 35
440) # # # 38 (C', I,
30235) p # // 71 (C,
I, 25040) r p w 74 (
C, I, 34180) // // #7
5 (C, I, 35870) // #
JF 112”11117

Claims (1)

[Scope of Claims] (1) An ink composition for gold inkjet recording, characterized in that it contains a water-soluble dye, a surfactant having a hydrophilic polyoxy-hydroxypropoxy group, and water. 2. The surfactant has the following general formula [1] or (II)
The ink composition for inkjet recording according to claim 1, which is a compound represented by: H (10ft-X(-011,Cl-1cJI,0-)-
H [The above R7 is an alkyl group, It is a water bulk atom or an alkyl group, R is an alkyl group or an aryl group, X is an oxygen atom or a sulfur atom, and n is 1 to 10
represents a positive integer. ]