JPH0218471A - ink - Google Patents

Abstract

PURPOSE:To obtain an ink containing a specific compound in the ink obtained by dispersing a pigment into a liquid medium consisting essentially of water, free from occurrence of clogging at the tip of a pen or olifice and suitable for ink jet recording system. CONSTITUTION:The aimed ink containing a compound expressed by the formula (R1-R3 are H, OH or alkyl; R4 and R5 are H or methyl; m and n are 1-30 and m+n is 2-50), preferably of 2-15wt.% in the ink obtained by dispersing a pigment in a liquid medium consisting essentially of water.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to ink used in various recording instruments such as writing utensils and printers, and particularly to inkjet recording in which recording is performed by ejecting a liquid droplet from an orifice of a recording head. The present invention relates to an ink suitable for the method.

(Conventional Technique vR) The inkjet recording method has the advantage that it generates little noise during recording, is easily compatible with color printing, and can obtain high-resolution recorded images at high speed.

In the inkjet recording method, the characteristics of the ink used are that physical properties such as viscosity and surface tension are within appropriate ranges, that the dissolved components have high dissolution stability, that they do not clog minute orifices, and that the concentration is sufficiently high. It is required that there be no change in physical properties or precipitation of solids during storage.

In addition to the above characteristics, recording can be performed without being restricted by the type of recording material, the fixing speed is high, and the recorded image has excellent light resistance, water resistance, and solvent resistance (especially alcohol resistance). In addition, properties such as providing recorded images with excellent resolution are also required.

Conventionally, water-soluble dyes have been mainly used as colorants for ink in inkjet recording systems because the liquid medium is water-based.By using water-soluble dyes, many of the above basic requirements of inkjet recording systems can be met. are satisfied. However, when using water-soluble dyes, these water-soluble dyes inherently have poor light resistance;
The light resistance of recorded images is often a problem. That is,
When a recorded image is exposed to sunlight, fluorescent light, or projector light, the recorded image may disappear, become illegible, or fade during long-term storage.

There is also a problem with the water resistance of recorded images. That is, images obtained using water-soluble dyes inherently have poor water resistance, and therefore, when exposed to water, the images may become unclear or disappear.

Therefore, in order to solve these problems caused by the use of water-soluble dyes, many inks using pigments instead of dyes have been proposed. For example, representative examples of research into dispersants for improving dispersion stability in the practical application of pigment inks include JP-A-60-118769;
-155280 Publication (Bentel), 61-23
5478 (Dainichiseika), etc., and examples of research on surface treatment of pigments include JP-A-59-120667 and JP-A-62-250084 (Bentel). Further, as examples of application to the inkjet recording method, Japanese Patent Application Laid-open Nos. 56-147859 to 147869, 56147871 to 147872, 56-157467 to 157468, and 57
-6791 Publication (Canon), No. 62-2747
No. 6, No. 62-74973 to No. 74974, (
(Pentel) etc.

Furthermore, regarding the improvement of clogging at the pen tip and orifice tip, which is one of the most important problems in inks using pigments as colorants, Japanese Patent Laid-Open Nos. 56-41261 (outer corner pigments) and 60 Nos. -51763 Publication, 60-7
The addition of urea and its derivatives, sorbitan, sorbitol, etc. has been proposed as in Japanese Patent No. 2968 and Japanese Patent No. 62-101672 (hereinafter referred to as Bentel).

However, despite the numerous studies mentioned above, the reality is that no ink has yet been proposed that satisfies all of the required performances, especially with regard to clogging properties.
When used as ink for inkjet recording method,
An ink that does not cause clogging at the tip of a fine orifice for a long period of time has not yet been developed, which poses a serious problem in terms of printer reliability.

Furthermore, improving storage stability is a major issue for pigment inks, and it is desired to develop inks that do not change physical properties or precipitate solids even after long-term storage.

Furthermore, in recent years there has been a strong demand for ink performance that is good for recording on plain paper, including paper specially prepared for inkjet recording, as well as copy paper, report paper, notebooks, and stationery commonly used in offices. There is a demand for an ink that has good fixing properties and can perform recording with good print quality.

However, conventional pigment inks often contain a large amount of surfactant for dispersion stabilization and/or defoaming, and therefore, when recording on plain paper, bleeding occurs in the printed area. There were cases where the quality deteriorated significantly.

Therefore, an object of the present invention is to provide an ink that does not cause clogging at the pen tip or the tip of a fine orifice for a long period of time even in an ink using a pigment as a colorant.

Another object of the present invention is to provide an ink that does not generate precipitates even during long-term storage.

Another object of the present invention is to prevent smearing not only on paper specially prepared for inkjet recording, but also on plain paper commonly used in offices such as copy paper, report paper, notebooks, and stationery. The object of the present invention is to provide an ink that provides good print quality.

(Means for solving problems) The above objects are achieved by the present invention as described below.

That is, the present invention is an ink formed by dispersing a pigment in a liquid medium containing water as a main component, which is characterized by containing a compound represented by the following formula (I).

mouth.

s (R, , R, and R3 in the formula represent a hydrogen atom, a hydroxyl group, or an alkyl group, R4 and R5 represent a hydrogen atom or a methyl group, m and n represent a numerical value of 1 to 30, and m + n is 2 (The numerical value is in the range of 50 to 50.) (Function) As a result of intensive studies on various ink compositions for improving the clogging property of pigment ink at the tip of the pen tip and the tip of the orifice, the inventor found that - Formula (I) It has been discovered that the addition of the compound represented by is effective in preventing the above-mentioned clogging.

In addition, the addition of such compounds is effective not only in improving clogging properties but also in improving storage stability, and furthermore, it suppresses the occurrence of ink bleeding on plain paper commonly used in offices. It was discovered that this method is also effective in improving printing quality, leading to the present invention.

According to the research of the present inventor, the compound represented by the formula (I) is a low vapor pressure substance and also has surfactant ability, so by adding it to the ink, it can prevent the evaporation of the liquid medium in the ink. It is also possible to prevent clogging and improve storage stability by suppressing the aggregation of pigments.

Furthermore, when printing on plain paper such as copy paper, report paper, notebook, stationery, etc., fixing properties can be improved without deteriorating print quality due to the surfactant ability of the compound represented by formula (I).

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.

General formula (I) used in the present invention and mainly characterizing the present invention
) Preferred specific examples of the compound represented by the formula include the following compounds, and the present invention is not limited thereto.
Exceeding this is not preferable because the viscosity of the resulting ink becomes too high. In addition, the compound of formula (I) may be a mixture in which m and n are different, and in that case, m and n are expressed as average values.

(Margin below) 2.3! jm4-C)13 2.3 Genhui 4-CH3 2,3 Beast 4-CH.

2.3 ■Base 4-CH3 2,3tH14-CH3 2,3 immediately 4-CH3 Secondary l3-CHf.

2! ffl-CHf fl-CH32t 2m-CH3 2 噸-〇, H.

21EH-nCJs 2 aperture □□□-CH3 Episode 2--CI (3 -OH -OH -OH -OH -OH -0H 2-0■ ■ ■ ■ -CH3 -C2H5 4-nC3H.

4-ic4He 4-C2H.

4-iC4H.

4-ics) It 4-ic, H.

-C113 -1cJ7 3-C2Hr.

3-H: 48g 4-icJ++ 4-ic2H5 -iCJs 2.3 earth 4-CI+3 2.1 direction 4-CH3 2nd and 3rd company base 4-CI+3 2.3tH14-C)I3 2.3U standing 4-CI+.

2.3U 4-CHl 2 Yuhui 3-CI+.

2nd grade assistant-C113 2 Yuhui 3-C113 2 immediately 3-CI+3 2R3-C211s 2 beast standing 3-ncJIs 2耘tt3-CI+3 2 Beast Bon 3-CI* -OH -OH -OH -OH -OH -OH I I ■ ■ ■ 4-CI+3 4-C, +15 4-nC,H.

4-iC4)19 4-C21-15 4-4cjl.

4-+C:Jl,.

4-ic3t17 4-+1;H3 4-iC3117 -C2H5 3-iC,)I9 4-icsH+ + 44-1C2H 54-iC4H The amount of the compound represented by formula (I) added to the ink is:
Although it varies depending on the colorant used and other liquid medium components used together, it is about 0.5 to 30% by weight in the ink, preferably 1 to 20% by weight, more preferably 2 to 15% by weight.
This is the proportion that accounts for If the amount added is less than 0.5% by weight, not only will the effect of suppressing evaporation of the ink liquid medium be insufficient, but also the storage stability will be improved by alleviating the aggregation of the pigment and the fixability on recording materials such as plain paper. The improvement is insufficient and the object of the present invention cannot be fully achieved. On the other hand, if the amount added exceeds 30% by weight, the viscosity of the ink increases, resulting in problems especially in terms of matching with an inkjet recording head.

Furthermore, it also gives a negative effect Δ on the drying properties of plain paper.

As the pigment used in the ink of the present invention, in addition to carbon black, almost all the organic pigments listed in the Dye Handbook and Color Index can be used. For example, azo pigments such as azo lake pigments, insoluble azo pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, atraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc. Examples include dye lakes such as cyclic pigments, basic dye lakes, and acid dye lakes; organic pigments such as nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments; and inorganic pigments such as titanium oxide and iron oxide. I can do it. Further, even if the pigment is not listed in the color index, any pigment that can be dispersed in the aqueous phase can be used in the present invention.

Furthermore, it is also possible to use the above-mentioned pigments surface-treated with surfactants, polymeric dispersants, etc., such as grafted carbon.

These pigments are generally about 0.5 for the inks of this invention.
It is used in a proportion of 20% by weight. It is preferably used in a range of 3 to 15% by weight.

Prior to preparing the ink of the present invention, the pigment is preferably subjected to a dispersion treatment using a conventionally known method together with a suitable dispersant, solvent, pure water and, if necessary, other additives.

As the dispersant, conventionally known polymer dispersants and surfactants used for dispersing pigments can be used.As the polymer dispersant, proteins such as gelatin, albumin, and casein, and natural rubbers such as gum arabic and gum tragacanth can be used. , glucosides such as saponin, cellulose derivatives such as methylcellulose, carboxycellulose, and hydroxymethylcellulose, natural polymers such as lignin sulfonate, shellac,
Polyacrylate, salt of styrene-acrylic acid copolymer, salt of vinylnaphthalene-acrylic acid copolymer, salt of styrene-maleic copolymer, salt of vinylnaphthalene-maleic acid copolymer, β-naphthalene sulfone Polymer dispersants such as anionic polymers such as sodium salts and phosphates of acid-formalin condensates, nonionic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene glycol, and surfactants such as fatty acid salts and high-grade polymers. Anionic surfactants such as alcohol sulfate ester salts, liquid fatty oil sulfate ester salts, alkylaryl sulfonates,
There are nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and polyoxyethylene sorbitan alkyl esters, and one or more of these may be selected as appropriate. Can be used. The amount used varies depending on the dispersant, but it is generally desirable to use 1 to 20% by weight based on the total amount of the ink.

On the other hand, the dispersing machine used for dispersing the pigment may be any general dispersing machine, and examples thereof include a ball mill, a roll mill, a sand mill, and the like. Among them, high-speed sand mills are preferred, such as super mills, sand grinders, bead mills, agitator mills, grain mills,
Examples include Dyno Mill, Pearl Mill, and Coball Mill (all trade names).

The ink of the present invention has the above-mentioned components as its main components, and is obtained by dissolving and dispersing them in a liquid medium containing water as its main component. Although water as a liquid medium can be used alone, it is generally preferable to use it in combination with an organic solvent. Examples of organic solvents used in combination include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 5ec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, and n-pen. Alkyl alcohols having 1 to 5 carbon atoms such as tanol; amides such as dimethylformamide and dimethylacetamide; ketone or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyethylene glycol, polypropylene glycol, etc. Polyalkylene glycols; ethylene glycol, propylene glycol, butylene gelicol, triethylene glycol, 1,2,6-hexandriol,
Alkylene glycols in which the alkylene group has 2 to 6 carbon atoms, such as thiodiglycol, hexylene glycol, diethylene glycol: Glycerin: ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monomethyl Lower alkyl ethers of polyhydric alcohols such as (or ethyl) ether; Lower dialkyl ethers of polyhydric alcohols such as triethylene glycol dimethyl (or ethyl) ether and tetraethylene glycol dimethyl (or ethyl) ether; sulfolane, N- Examples include methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone. Among these many 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.

The content of the water-soluble organic solvent is generally 2 to 40% by weight, preferably 5 to 2% by weight based on the total weight of the ink.
The range is 0%.

The essential components of the ink of the present invention are as described above, but various other surfactants, viscosity modifiers, surface tension modifiers, binder resins, etc. to improve the fixing properties of the ink on the recording material are also added. It can be added as needed.

For example, viscosity modifiers or binders such as polyvinyl alcohol, celluloses, and water-soluble resins; various cationic, anionic, or nonionic surfactants; surfactants such as secondary alcohols and/or their ethylene oxide adducts; jetanol; Examples include surface tension adjusters such as amines and triethanolamine; pH adjusters using a buffer solution, antifungal agents, and the like.

In addition, in order to prepare ink used in inkjet recording methods that charge the ink, lithium chloride,
A resistivity adjuster such as inorganic salts such as ammonium chloride and sodium chloride is added.

When applied to an inkjet recording method in which ink is ejected by the action of thermal energy, thermal physical property values (e.g., specific heat, coefficient of thermal expansion, thermal conductivity, etc.)
In addition, the ink of the present invention has a surface tension of 25 to 65 dyn at 25°C as an ink physical property from the viewpoint of matching with writing instruments and inkjet recording heads.
It is desirable to adjust the viscosity to 15 cps or less, preferably 10 cps or less, more preferably 5 cps or less.

The ink of the present invention obtained as described above solves the problems of the prior art, and in particular, despite using a pigment as a coloring agent, it can be used for a long period of time at the tip of a pen or fine orifice. It does not clog over time, and there is almost no precipitation of solids even after long-term storage, and it can be used not only on paper specially prepared for inkjet recording, but also on copy paper, report paper, notebooks, and stationery. Even on plain paper commonly used in offices such as the following, it is possible to record with good fixing properties and excellent printing quality without bleeding.

(Example) Next, the present invention will be explained in more detail by giving examples and comparative examples. In the text, parts or percentages are based on weight unless otherwise specified.

Examples 1 to 5 The following components were dispersed in a pearl mill (manufactured by Ashizawa ■), and the resulting dispersion was centrifuged to remove coarse particles (manufactured by Hitachi Seisakusho) to obtain inks A to E of the present invention. Obtained.

Next, using the obtained inks A to E, an inkjet printer BJ-80 (trade name: manufactured by Canon ■), which uses a heating element as an ink ejection energy source, was used as an inkjet recording device to evaluate clogging properties. Storage stability evaluation and fixation evaluation were performed. The above evaluations are shown in Table 1 below.

Lλ Gen A Compound of general formula (I) (No. 1) 7 parts carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation)
10 parts styrene-maleic anhydride copolymer (molecular weight 10.000, acid value 175)
7 parts ethylene glycol
15 parts ethanolamine 1
Nikkor TS-30 (manufactured by Nikko Chemicals)
2 parts water
55 parts Ink B Compound of formula (I) (No. 5) 4 parts Quinacridone Red (manufactured by Fuji Shiki) 9 parts Styrene-acrylic acid copolymer (molecular weight 11.000, acid value 150)
6-part aminomethyl propatool
1 part glycerin 10 parts Nikkor BL-9EX (manufactured by Nikko Chemicals) 0.
5 parts Water 63.5 parts Eno Gentan Compound of formula (I) (No. 16) 4 parts Phthalocyanine Blue (manufactured by Toyo Ink) 8 parts α-methylstyrene-styrene-acrylic acid copolymer (
molecule! 12,500, acid value 197) 5 parts ethylene glycol 5 parts glycerin
10 parts jetanolamine
1 part Nikkor MYL-10 (manufactured by Nikko Chemicals) 0.5 parts water 62.5 parts Compound of general formula (I) (No. 24) 5 parts Carbon black (MCF-88, manufactured by Mitsubishi Chemical Corporation) )
9 parts styrene-acrylic acid copolymer (molecular weight 10.000, acid value 195)
7 parts N-methyl-jetanolamine 1 part glycerin 13 parts ethanol 5 parts water
57 parts A'2 Compound of general formula (I) (No. 43) 6 parts Hansa Yellow 3G 5 parts Polyoxyethylene alkyl ether phosphate
2nd part sorbit
5 parts ethylene glycol
7 parts diethylene glycol 10
Nikkor NP-7.5 (manufactured by Nikko Chemicals)
1 part water
62 parts Comparative Examples 1 to 5 Example 1 was prepared by removing the compound of general formula (1) in Inks A to E of Examples 1 to 5 and replacing the content with water.
Comparative inks F to J were obtained in the same manner as above.

Comparative Example 6 Comparative ink K was obtained in the same manner as in Example 4 except that the compound of formula (I) in the components of Ink D of Example 4 was replaced with urea.

Comparative Example 7 Comparative ink L was obtained in the same manner as in Example 4 except that the compound of formula (I) in the components of ink D of Example 4 was replaced with sorbitol.

Next, using the obtained ink, clogging property evaluation and printing quality evaluation were performed in the same manner as in Examples, and the results are shown in Table 1 below.

Comparative Example 8 Comparative Ink M was obtained in the same manner as in Example 4 except that the compound of Formula (I) in the components of Ink D of Example 4 was replaced with polyethylene glycol (molecular weight 500).

Next, using the obtained ink, clogging property evaluation and printing quality evaluation were performed in the same manner as in Examples, and the results are shown in Table 1 below.

In Clogging resistance 11 Storage stability 62 Fixability 13 B.C.D.E. ○ OOO○ ○　　ooo.

ooooo.

One inch per side FGHIJKLM clogging resistance
X X X X X Q △ △ Storage stability 92× Δ Δ × × Δ Δ X Fixability 83
△××△××× Conditions = 40℃, lO±5%RH
) After performing the recovery operation for nozzle clogging, alphanumeric characters were printed again and judged based on the number of recovery operations and the presence or absence of defects such as faded or missing characters.

O: Printing equivalent to the initial state is possible after 0 to 5 recovery operations.

Δ: Printing equivalent to the initial level is possible after 6 to 10 recovery operations.

x: Printing 2 equivalent to the initial one after 10 recovery operations Umbrella 3 characters are possible.

Put 80cc of storage stability evaluation ink into a shot bottle (manufactured by Duran),
It was stored in an oven at 50°C for one month. After the sample was returned to room temperature, the bottle was turned upside down and the precipitate adhering to the bottle wall was evaluated.

O: Almost no precipitate.

△: A little precipitate was generated.

×: A large amount of precipitate was generated.

Fixability evaluation 10 seconds after printing on commercially available copy paper and bond paper, 30
After a few seconds, the printed area was rubbed with a filter paper (trade name: No. 5G, manufactured by Toyo Kagaku Sangyo ■).

(25℃, 60% R1 (evaluated under environmental conditions) O: 10
Almost no fading in seconds Δ: Small fading in 30 seconds Large fading in 30 seconds (Effect) As explained above, according to the present invention, even in ink that uses pigments as colorants, pen tips and minute This enables highly reliable recording without clogging at the orifice tip for a long period of time.

Further, the ink of the present invention shows no change in physical properties or precipitation of solid content even after long-term storage, and is excellent in stability.

Furthermore, the ink of the present invention has good fixing properties and prints not only on paper specially prepared for inkjet use, but also on plain paper commonly used in offices such as copy paper, report paper, notebooks, and stationery. Records with excellent quality can be obtained.

Claims (1)

[Claims] (1) An ink comprising a pigment dispersed in a liquid medium containing water as a main component, which is characterized by containing a compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (R_1, R_2, and R_3 in the formula represent a hydrogen atom, a hydroxyl group, or an alkyl group, R_4 and R_5 represent a hydrogen atom or a methyl group, and m and n are 1 It represents a numerical value from 30 to 30, and m+n is a numerical value in the range from 2 to 50.)