JP2021024973A - Ink, ink storage container, recording device, recording method, and recorded matter - Google Patents

Abstract

To solve the following problem in which, although inks are conventionally disclosed which comprise a pigment dispersion, a polysiloxane surfactant, polyurethane resin particles, and dipropylene glycol monomethyl ether, images formed by using such inks fall short of beading properties and adhesion.SOLUTION: An ink comprises: a polyether-modified siloxane compound expressed by the predetermined general formula (1); a urethane resin; and a color material.SELECTED DRAWING: None

Description

The present invention relates to ink, an ink container, a recording device, a recording method, and a recorded material.

Inkjet recording devices have advantages such as low noise, low running cost, and easy color printing, and are widely used in general households as digital signal output devices. Further, in recent years, inkjet technology has been used not only for home use but also for commercial use and industrial use. In commercial and industrial applications, coated paper (coated paper) for printing with low ink absorption and plastic media with non-ink absorption are used as recording media. Therefore, these media can also be used by the inkjet recording method. , It is required to realize image quality comparable to that of conventional offset printing.

Patent Document 1 discloses an ink containing a pigment dispersion, a polysiloxane surfactant, and polyurethane resin particles in Examples.

An object of the present invention is to provide an ink that can obtain an image having excellent beading property and adhesion.

The invention according to claim 1 is an ink containing a polyether-modified siloxane compound represented by the following general formula (1), a urethane resin, and a coloring material.

(In the general formula (1), R represents a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms, and a, b, c, n, and m are (a + b + c) / (n + m) ≧ 0.5. Fulfill.)

According to the present invention, it is possible to provide an ink that can obtain an image having excellent beading property and adhesion.

FIG. 1 is a perspective explanatory view showing an example of a recording device. FIG. 2 is a perspective explanatory view showing an example of the main tank.

Hereinafter, an example of the embodiment of the present invention will be described.

<< Ink >>
The ink of the present embodiment contains a polyether-modified siloxane compound represented by the general formula (1), a urethane resin, and a coloring material, and if necessary, an organic solvent, water, a resin other than the urethane resin, and others. Additives may be included.

<Polyether-modified siloxane compound represented by the general formula (1)>
The polyether-modified siloxane compound contained in the ink is a compound represented by the following general formula (1), and is preferably used as a surfactant. When the ink contains the polyether-modified siloxane compound represented by the general formula (1), the beading property is improved in the image formed by the ink. The polyether-modified siloxane compound represented by the general formula (1) may be used alone or in combination of two or more.

R in the general formula (1) represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is preferably a hydrogen atom.

Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Group etc. can be mentioned.

A, b, c, n, and m in the general formula (1) represent numerical values, satisfy the following formula "(a + b + c) / (n + m) ≧ 0.5", and "2.0 ≧ (a + b + c) / ( It is preferable that "n + m) ≥ 0.5", more preferably "1.5 ≥ (a + b + c) / (n + m) ≥ 0.5", and "1.0 ≥ (a + b + c) / (n + m) ≥". It is more preferably 0.5 ". Since the polyether-modified siloxane compound satisfying "(a + b + c) / (n + m) ≥ 0.5" can improve the wettability of the ink containing this compound with respect to the recording medium, the image formed by the ink is bee. Dingability is improved.
Further, in the general formula (1), "a + b + c + n + m" is preferably 500 or less, more preferably 100 or less, and further preferably 50 or less.

The molecular weight of the polyether-modified siloxane compound represented by the general formula (1) is preferably 2000 or more and 30,000 or less, and more preferably 2000 or more and 5000 or less.

The content of the polyether-modified siloxane compound represented by the general formula (1) is preferably 0.1% by mass or more and 4.0% by mass or less, and 1.0% by mass or more and 2.0 by mass, based on the amount of ink. More preferably, it is by mass or less. When it is 0.1% by mass or more and 4.0% by mass or less, the adhesion of the image to the impermeable substrate is improved and the image quality such as image gloss is also improved when used in combination with the urethane resin.

<Urethane resin>
The ink contains urethane resin. By containing the urethane resin, it is possible to impart high image glossiness, scratch resistance, and adhesion to the image formed by the ink. In order to further impart these functions, the urethane resin is preferably used as urethane resin particles in the ink. Examples of the urethane resin include a polyether polyurethane resin, a polycarbonate polyurethane resin, and a polyester polyurethane resin.

As the urethane resin, a manufactured product or a commercially available product may be used. Examples of commercially available products include U-coat UX-485 (polycarbonate-based polyurethane resin particles), U-coat UWS-145 (polycarbonate-based polyurethane resin particles), Permarin UA-368T (polycarbonate-based polyurethane resin particles), and Permarin UA-200 (polyether). Polyurethane resin particles) (above, manufactured by Sanyo Kasei Kogyo Co., Ltd.) and the like. These may be used alone or in combination of two or more.

The content of the urethane resin is not particularly limited, but is preferably 12.0% by mass or less, and more preferably 8.5% by mass or less of the amount of ink from the viewpoint of improving dispersibility. Further, when the content is 8.5% by mass or less, an image having high glossiness and excellent image gloss can be obtained, which is preferable. Further, from the viewpoint of enhancing the scratch resistance of the image formed by using the ink, the content of the urethane resin is preferably 5.0% by mass or more of the total amount of the ink.

-Various materials used in the production of urethane resin-
The urethane resin can be obtained, for example, by reacting a polyol with a polyisocyanate.

--Polycarbonate ---
Examples of the polyol include polyether polyols, polycarbonate polyols, polyester polyols and the like. These may be used alone or in combination of two or more.
The urethane resin is preferably a polycarbonate-based urethane resin obtained by using a polycarbonate polyol. Since the carbonate group has a high cohesive force, the ink containing the polycarbonate urethane resin is excellent in water resistance, heat resistance, abrasion resistance, weather resistance, and scratch resistance. Therefore, the ink containing the polycarbonate-based urethane resin is suitable for ink applications used in harsh environments such as outdoor applications.

Examples of the polyether polyol include those obtained by addition polymerization of an alkylene oxide using at least one compound having two or more active hydrogen atoms as a starting material.
Examples of the compound having two or more active hydrogen atoms include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylolglycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol. , Glycerin, trimethylolethane, trimethylolpropane and the like. These may be used alone or in combination of two or more.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran. These may be used alone or in combination of two or more.
Specifically, as the polyether polyol, polyoxytetramethylene glycol, polyoxypropylene glycol and the like are preferable. By using these, a urethane resin as an ink binder that can impart excellent scratch resistance can be obtained.

Examples of the polycarbonate polyol include those obtained by reacting a carbonic acid ester with a polyol, those obtained by reacting phosgene with bisphenol A, and the like. These may be used alone or in combination of two or more.
Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like. These may be used alone or in combination of two or more.
Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2. -Butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcin, Relatively low molecular weight dihydroxy compounds such as bisphenol-A, bisphenol-F, 4,4'-biphenol; polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol; polyhexamethylene adipate, polyhexamethylene succi Examples thereof include polyester polyols such as nate and polycaprolactone. These may be used alone or in combination of two or more.

Examples of the polyester polyol include those obtained by esterifying a low molecular weight polyol and a polycarboxylic acid, polyesters obtained by ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone, and copolymerized polyesters thereof. And so on. These may be used alone or in combination of two or more.
Examples of the low molecular weight polyol include ethylene glycol and propylene glycol. These may be used alone or in combination of two or more.
Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecandicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, anhydrides or ester-forming derivatives thereof. These may be used alone or in combination of two or more.

--Polyisocyanate ---
Examples of the polyisocyanate include aromatic diisocyanates such as phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. Examples thereof include aliphatic or alicyclic diisocyanates such as isocyanate and 2,2,4-trimethylhexamethylene diisocyanate. These may be used alone or in combination of two or more. Among these, it is preferable to use an alicyclic diisocyanate from the viewpoint that an image having long-term weather resistance can be formed when the ink is used for outdoor applications such as posters and signboards. Further, by using the alicyclic diisocyanate, the intensity of the image is improved and excellent scratch resistance can be obtained. Examples of the alicyclic diisocyanate include isophorone diisocyanate and dicyclohexylmethane diisocyanate. The content of the alicyclic diisocyanate is preferably 60.0% by mass or more with respect to the total amount of polyisocyanate.

-Urethane resin manufacturing method-
The urethane resin can be obtained by a conventionally commonly used production method, and examples thereof include the following methods.
First, the above-mentioned polyol and the above-mentioned polyisocyanate are reacted at an equivalent ratio in which the isocyanate group becomes excessive in the absence of a solvent or in the presence of an organic solvent to produce an isocyanate-terminated urethane prepolymer. The anionic groups in the isocyanate-terminated urethane prepolymer are then neutralized with a neutralizing agent, if necessary, then reacted with a chain extender, and finally the organic solvent in the system is removed if necessary. Obtain urethane resin.

--Organic solvent ---
Examples of the organic solvent that can be used for producing the urethane resin include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic acid esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; dimethylformamide, Examples thereof include amides such as N-methylpyrrolidone and N-ethylpyrrolidone. These may be used alone or in combination of two or more.

--Chain extender ---
Examples of the chain extender include polyamines and other active hydrogen group-containing compounds.
Examples of polyamines include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazin, isophoronediamine, 4,4'-dicyclohexylmethanediamine, and 1,4-cyclohexanediamine. Diamines such as; polyamines such as diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazines such as hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine; dihydrazide succinate, dihydrazide adipic acid, etc. Examples thereof include dihydrazides such as glutarate dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide. These may be used alone or in combination of two or more.
Examples of other active hydrogen group-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and saccharose. , Methylene glycol, glycerin, sorbitol and other glycols; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone and other phenols. ; Water and the like. These may be used alone or in combination of two or more as long as the storage stability of the ink is not deteriorated.

-Urethane resin condition-
As described above, the urethane resin is preferably present in the ink in the form of urethane resin particles. Such ink is preferably obtained by mixing it with a material such as a coloring material or an organic solvent in the state of a resin emulsion in which water is dispersed as a dispersion medium. By blending an organic solvent, a coloring material, water, or the like in the state of a resin emulsion to prepare an ink, the ease of work and uniform dispersibility are improved.

The urethane resin particles are dissolved in an organic solvent added to the ink to form a film to form a film-like recording layer (image). That is, the film formation of urethane resin particles is promoted by evaporating water from the ink after the ink is applied. Therefore, depending on the type of urethane resin particles used, it is possible to perform recording without a heating step.

The method for dispersing the urethane resin particles in water is not particularly limited, but for example, a method using self-emulsifying resin particles having an anionic group in the molecular structure and a forced emulsifying resin particles using a dispersant. Examples include a method using. Among these, a method using self-emulsifying resin particles having an anionic group in the molecular structure is preferable from the viewpoint of increasing the strength of the recorded material.

When self-emulsifying urethane resin particles are used, the acid value of the anionic group is preferably 5 mgKOH / g or more and 100 mgKOH / g or less from the viewpoint of water dispersibility, scratch resistance, and chemical resistance, and is 5 mgKOH / g. More preferably, it is mg or more and 50 mgKOH / mg or less.

Examples of the anionic group include a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group and the like. Among these, carboxylate groups and sulfonate groups, which are partially or wholly neutralized with a basic compound or the like, are preferable from the viewpoint of maintaining good water dispersion stability. In order to introduce an anionic group into the resin, a monomer having an anionic group may be used.
Further, the anionic group is preferably neutralized with a basic compound. Examples of the basic compound include organic amines such as ammonia, triethylamine, pyridine and morpholine; alkanolamines such as monoethanolamine; and metal base compounds containing Na, K, Li, Ca and the like. These may be used alone or in combination of two or more.

Examples of the method for producing an aqueous dispersion using the forced emulsification type urethane resin particles include a method using a surfactant such as a nonionic surfactant and an anionic surfactant. These may be used alone or in combination of two or more. Among these, a method using a nonionic surfactant is preferable from the viewpoint of water resistance.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, and sorbitan. Examples thereof include fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ethers, polyoxyethylene alkylamines, alkyl alkanolamides, and polyalkylene glycol (meth) acrylates. Among these, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine are preferable. These may be used alone or in combination of two or more.

Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurilates, sulfosuccinates, ether sulfonates, and ether carboxylic acids. Examples thereof include acid salts, fatty acid salts, naphthalene sulfonic acid formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, and alkylamine oxides. Among these, polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferable.

When an aqueous dispersion is produced using forced emulsified urethane resin particles, the content of the surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. However, forced emulsified urethane resin It is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less with respect to the total amount of particles. When the content is in the range of 0.1% by mass or more and 30% by mass or less, urethane resin particles are preferably formed into a film, an ink having excellent adhesion and water resistance can be obtained, and the recorded material is blocked. It is preferably used.

-Various physical characteristics of urethane resin-
The volume average particle diameter of the urethane resin particles is preferably 10 nm or more and 1,000 nm or less, more preferably 10 nm or more and 500 nm or less, and further preferably 10 nm or more and 200 nm or less, considering that it is used in an inkjet recording device. When the volume average particle diameter is 10 nm or more and 1,000 nm or less, the contact portion between the organic solvent and the surface of the urethane resin particles increases, the film-forming property of the urethane resin particles is enhanced, and a continuous coating of tough resin is formed. Therefore, a high-strength recorded material can be obtained. The volume average particle size can be measured using, for example, a particle size analyzer (Microtrack MODEL UPA9340, manufactured by Nikkiso Co., Ltd.).

As for the qualitative and quantitative analysis of resins, for example, "Test method and evaluation result of each dynamic property of plastic materials (22); by Takeo Yasuda, Plastics: Journal of Japan Plastics Industry Federation /" Plastics "Editorial Committee" It can be confirmed by the procedure as described in detail. Specifically, it can be confirmed by analysis by infrared spectroscopic analysis (IR), thermal analysis (DSC, TG / DTA), thermal decomposition gas chromatography (PyGC), nuclear magnetic resonance (NMR), or the like.

The glass transition temperature of the urethane resin can be measured using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments, Inc.). Specifically, the measurement is performed under the conditions of the following continuous temperature programs 1 to 4, and the value measured by the temperature program 3 is defined as the glass transition temperature. The measured value of the temperature program 3 is used in order to ensure the reproducibility of the measured value.
Temperature program:
(1) 30 ° C or higher and 250 ° C or lower: heating rate 30 ° C / min, holding time 1 minute (2) 250 or higher and -100 ° C or lower: cooling rate 30 ° C / min, holding time 30 minutes (3) -100 or higher 250 ° C or lower: heating rate 5 ° C / min, holding time 1 minute (4) 250 or more and 30 ° C or lower: cooling rate 30 ° C / min, holding time 2 minutes

The minimum film-forming temperature of the urethane resin (hereinafter, also referred to as "MFT") is not particularly limited. However, when the minimum film-forming temperature exceeds 80 ° C., it is preferable to heat the ink after application from the viewpoint that the image fastness can be improved without the resin film-forming defect.
When adjusting the minimum film-forming temperature, for example, it can be adjusted by controlling the glass transition temperature of the urethane resin (hereinafter, also referred to as "Tg"), and when the urethane resin is a copolymer. Can be adjusted by changing the ratio of the monomers forming the copolymer. The minimum film forming temperature is the minimum temperature at which a transparent continuous film is formed when the urethane resin is thinly cast on a metal plate such as aluminum and the temperature is raised. In the temperature range below the film temperature, the emulsion becomes a white powder. The minimum film-forming temperature is measured by, for example, a commercially available minimum film-forming temperature measuring device such as "film-forming temperature test device" (manufactured by Imoto Seisakusho Co., Ltd.) and "TP-801 MFT tester" (manufactured by Tester Sangyo Co., Ltd.). be able to. Further, since the minimum film-forming temperature changes depending on the volume average particle size of the resin, the minimum film-forming temperature of the resin can be set as a target value by a control factor of the volume average particle size of the resin.

<Color material>
The ink of this embodiment contains a coloring material. The coloring material is not particularly limited, and pigments and dyes can be used. As the pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Further, a mixed crystal may be used as the pigment.

As the pigment, for example, black pigment, yellow pigment, magenta pigment, cyan pigment, white pigment, green pigment, orange pigment, glossy color pigment such as gold or silver, metallic pigment and the like can be used.
As inorganic pigments, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, carbon black produced by known methods such as contact method, furnace method, and thermal method. Can be used.
Examples of organic pigments include azo pigments and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , Dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), nitro pigment, nitroso pigment, aniline black and the like can be used. Among these pigments, those having a good affinity with a solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.

As a specific example of the pigment, for black, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, or copper, iron (CI pigment black 11) , Metals such as titanium oxide, and organic pigments such as aniline black (CI pigment black 1).
Further, for color, C.I. I. Pigment Yellow 1,3,12,13,14,17,24,34,35,37,42 (yellow iron oxide), 53,55,74,81,83,95,97,98,100,101,104 , 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmin 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Magenta), 104, 105, 106, 108 ( Cadmium Red), 112, 114, 122 (Quinacridone Magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3, 15: 4 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment Greens 1, 4, 7, 8, 10, 17, 18, 36, etc.

The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone or two or more types may be used in combination.
As a dye, for example, C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52,80,82,249,254,289, C.I. I. Acid Blue 9,45,249, C.I. I. Acid Black 1,2,24,94, C.I. I. Hood Black 1, 2, C.I. I. Direct Yellow 1,12,24,33,50,55,58,86,132,142,144,173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct Blue 1,2,15,71,86,87,98,165,199,202, C.I. I. Dilekdo Black 19,38,51,71,154,168,171,195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive Black 3, 4, 35 can be mentioned.

The content of the coloring material in the ink is preferably 0.1% by mass or more and 15.0% by mass or less, more preferably 1.0% by mass, from the viewpoint of improving the image density, good adhesion and ejection stability. It is 10.0% by mass or less.

As a method of dispersing the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing it, and a method of dispersing using a dispersant are used. The method, etc. can be mentioned.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) so that the pigment can be dispersed in water. Can be mentioned.
Examples of the method of coating the surface of the pigment with a resin and dispersing the pigment include a method of encapsulating the pigment in microcapsules so that the pigment can be dispersed in water. This can be rephrased as a resin coating pigment. In this case, not all the pigments to be blended in the ink need to be coated with the resin, and the uncoated pigments or the partially coated pigments may be dispersed in the ink.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and the like can be used depending on the pigment.
As the dispersant, RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd. and a naphthalene sulfonate Na formalin condensate can also be preferably used as the dispersant.
The dispersant may be used alone or in combination of two or more.

<Pigment dispersion>
It is possible to obtain an ink by mixing a material such as water or an organic solvent with a pigment. It is also possible to produce an ink by mixing a material such as water or an organic solvent with a pigment dispersion obtained by mixing a pigment and other water or a dispersant.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. It is preferable to use a disperser for dispersion.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency is 20 nm or more in terms of the maximum number because the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high. It is preferably 500 nm or less, more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and can be appropriately selected depending on the intended purpose, but is 0.1% by mass from the viewpoint of obtaining good ejection stability and increasing the image density. It is preferably 50% by mass or more, and more preferably 0.1% by mass or more and 30% by mass or less.
It is preferable to degas the pigment dispersion by filtering the coarse particles with a filter, a centrifuge, or the like, if necessary.

<Organic solvent>

The organic solvent used for the ink is not particularly limited, but a liquid organic solvent at 25 ° C. and 1 atm can be preferably used. For example, ethers such as polyhydric alcohols, polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines and sulfur-containing compounds can be used.

Specific examples of the organic solvent include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and the like. 2,3-Butanediol, 3-Methyl-1,3-Butanediol, Triethylene glycol, Polyethylene glycol, Polypropylene glycol, 1,2-Pentanediol, 1,3-Pentanediol, 1,4-Pentanediol, 2 , 4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1, Polyhydric alcohols such as 3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. Polyhydric alcohol alkyl ethers, ethylene glycol monophenyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1 , 3-Dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone and other nitrogen-containing heterocyclic compounds, formamide, N-methylformamide and other amides, monoethanolamine, diethanolamine, triethylamine and other amines, dimethyl Examples thereof include sulfur-containing compounds such as sulfoxide, sulfolane and thiodiethanol, propylene carbonate and ethylene carbonate.

As the organic solvent, a polyol compound having 8 or more carbon atoms and a glycol ether compound are also preferably used. Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of the glycol ether compound include polyvalent alcohol alkyls such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. Ethers: Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether can be mentioned.
The polyol compound and glycol ether compound having 8 or more carbon atoms can improve the permeability of the ink when paper is used as the recording medium.

The content of the organic solvent in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of ink drying property and ejection reliability, 10.0% by mass with respect to the total amount of ink. More than 60.0% by mass is preferable, and 20.0% by mass or more and 60.0% by mass or less is more preferable.

-Compound represented by the general formula (1)-
As the organic solvent, a compound represented by the following general formula (2) is also preferably used. By containing the compound represented by the general formula (2) in the ink, the beading property of the ink can be improved even when a non-permeable recording medium is used as the recording medium to which the ink is applied.
In the general formula (2), R ₁ , R ₂ , and R ₃ independently represent hydrocarbon groups having 1 or more and 8 or less carbon atoms. Specific examples thereof include 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide and the like.
The content of the compound represented by the general formula (2) is preferably 1.0% by mass or more and 20.0% by mass or less with respect to the total amount of the ink, and is 1.0% by mass or more and 10. It is more preferably 0% by mass or less, and further preferably 5.0% by mass or more and 10.0% by mass or less.
The mass ratio of the content of the compound represented by the general formula (2) to the polyether-modified siloxane compound represented by the general formula (1) (general formula (2) / general formula (1)) is 1. It is preferably 5 or more and 15.0 or less, and more preferably 1.0 or more and 10.0 or less.

<Water>
The ink of this embodiment preferably contains water. The water content in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of ink drying property and ejection reliability, 10% by mass or more and 90% by mass with respect to the total amount of ink The following is preferable, and 20% by mass or more and 60% by mass or less is more preferable.

<Additives>
If necessary, an antifoaming agent, an antiseptic antifungal agent, a rust preventive agent, a pH adjusting agent and the like may be added to the ink.

-Defoamer-
The defoaming agent is not particularly limited, and examples thereof include a silicone-based defoaming agent, a polyether-based defoaming agent, and a fatty acid ester-based defoaming agent. These may be used alone or in combination of two or more. Among these, a silicone-based defoaming agent is preferable because it has an excellent defoaming effect.

-Preservatives and fungicides-
The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

-Rust inhibitor-
The rust preventive is not particularly limited, and examples thereof include acidic sulfites and sodium thiosulfate.

-PH regulator-
The pH adjusting agent is not particularly limited as long as the pH can be adjusted to 7 or more, and examples thereof include amines such as diethanolamine and triethanolamine.

<Physical characteristics of ink>
The physical characteristics of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity, surface tension, pH and the like are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 5 mPa · s or more and 30 mPa · s or less, preferably 5 mPa · s or more and 25 mPa · s or less, from the viewpoint of improving the print density and character quality and obtaining good ejection properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'x R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less, more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is preferably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12, more preferably 8 to 11, from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

<Recording medium>
The recording medium is not particularly limited, and plain paper, glossy paper, special paper, cloth, or the like can be used, but good image formation can be achieved even if a non-permeable base material is used.
The non-permeable base material is a base material having a surface having low water permeability and low absorbability, and includes a material that does not open to the outside even if there are many cavities inside, and more quantitatively, A substrate having a water absorption of 10 mL / m ² or less from the start of contact to 30 msec ^{1/2 in the Bristow method.}
As the non-permeable base material, for example, a plastic film such as a vinyl chloride resin film, a polyethylene terephthalate (PET) film, polypropylene, polyethylene, or a polycarbonate film can be preferably used.

Examples of non-permeable substrates using polypropylene and polyethylene include AR1025, AR1056, AR1082, EC1082, 1082D, 1073D, 1056D, 1025D, FR1073 (Asahi DuPont Flashspan Products Co., Ltd.), P2002, P2102, P2108, P2161, P2171, P2111, P4266, P5767, P3162, P6181, P8121, P1162, P1111, P1128, P1181, P1153, P1157, P1146, P1147, P1171 (Toyo Spinning Co., Ltd.), YPI, Aqua Yupo, Super Yupo, Ultra Yupo, New Yupo Examples include Yupo lighting paper, Yupo building material paper, Yupo high gloss, Yupo jet, and metallic Yupo (Yupo Corporation).

<< Recorded material >>
The recording material has a recording medium and a printing layer formed on the recording medium, and has other layers as needed. Since the printing layer is formed using the ink of the present embodiment, it contains the polyether-modified siloxane compound represented by the general formula (1), the urethane resin, and the coloring material contained in the ink.

<< Recording device, recording method >>
The ink of the present embodiment can be suitably used for various recording devices by the inkjet recording method, for example, a printer, a facsimile device, a copying device, a printer / fax / copier multifunction device, a three-dimensional modeling device, and the like.
The recording device and the recording method are devices capable of ejecting ink, various processing liquids, and the like to a recording medium, and a method of recording using the device. The recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means related to feeding, transporting, and discharging paper of a recording medium, and other devices called pretreatment devices and posttreatment devices. ..
The recording device and recording method may include a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the print surface and the back surface of the recording medium. The heating means and the drying means are not particularly limited, but for example, a hot air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
When an infrared heater is used as the heating means and the drying means, at least a near infrared irradiation device is provided. As a near-infrared irradiation device, a device including a halogen lamp and a reflection mirror is known. A halogen heater is built into the reflection mirror and made into a heating unit to realize efficient heating. For example, UH-USC-CL300, UHUSC-CL700, UH-USC-CL1000, UH -USD-CL300, UHUSD-CL700, UH-USD-CL1000, UH-MA1-CL300, UHMA1-CL700, UH-MA1-CL1000 (all manufactured by Ushio, Inc.) and the like.
Further, the recording device and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those that form patterns such as geometric patterns and those that form a three-dimensional image are also included.
Further, the recording device includes both a serial type device that moves the discharge head and a line type device that does not move the discharge head, unless otherwise specified.
Further, as this recording device, it is possible to use not only a desktop type but also a wide recording device capable of printing on an A0 size recording medium, or, for example, continuous paper wound in a roll shape as a recording medium. A continuous line printer is also included.

An example of the recording device will be described with reference to FIGS. 1 and 2. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanical unit 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink container 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is packaged with, for example, an aluminum laminate film. It is formed of members. The ink container 411 is housed in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided behind the opening when the cover 401c of the main body of the apparatus is opened. A main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink ejection port 413 of the main tank 410 and the ejection head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be ejected (applied) from the ejection head 434 to the recording medium. ..

The method of using the ink is not limited to the inkjet recording method, and can be widely used. In addition to the inkjet recording method, examples thereof include a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, and a spray coating method.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Example of preparation of pigment dispersion>
After premixing the following formulation mixture, it is circulated and dispersed for 7 hours in a disc type bead mill (manufactured by Simmal Enterprises Co., Ltd., KDL type, media: using zirconia balls with a diameter of 0.3 mm) to self-disperse black pigment dispersion. (Pigment solid content concentration: 15% by mass) was obtained.
-Carbon black pigment (trade name: Monarch800, manufactured by Cabot Corporation): 15.0 parts by mass-Anionic surfactant (trade name: Pionin A-51-B, manufactured by Takemoto Oil & Fat Co., Ltd.): 2.0 parts by mass- Ion-exchanged water: 83.0 parts by mass

<Synthesis example of polyether-modified siloxane compound>
-Synthesis example of polyether-modified siloxane compound 1-
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 400 g of ethylene glycol allyl methyl ether and 0.5 g of a 0.5 mass% toluene solution of chloroplatinic acid were charged and replaced with nitrogen gas. After heating the inside of the reaction vessel to 70 ° C., 400 g of hexadecamethyloctasiloxane having hydrogen atoms at both ends of the siloxane chain was added dropwise over 30 minutes. Next, the inside of the reaction vessel was heated to 110 ° C. and held for 3 hours with stirring to react the above materials. After completion of the reaction, the low boiling point was distilled off under reduced pressure to obtain a polyether-modified siloxane compound 1. As a result of structural analysis by NMR, the polyether-modified siloxane compound 1 was found to be a + b + c = 20, m = 0, n = 10, (a + b + c) / (n + m) = 2.0.

-Example of synthesis of polyether-modified siloxane compound 2-
By the same method as in the synthesis example of polyether-modified siloxane compound 1, 150 g of octamethylheptantetrasiloxane having two hydrogen atoms bonded to the central silicon atom was used instead of hexadecamethyloctasiloxane. A polyether-modified siloxane compound 2 was obtained. As a result of structural analysis by NMR, the polyether-modified siloxane compound 2 was found to be a + b + c = 10, m = 0, n = 20, (a + b + c) / (n + m) = 0.5.

-Synthesis example of polyether-modified siloxane compound 3-
Polyether-modified except that the amount of ethylene glycol allylmethyl ether added was 300 g and 200 g of heptamethyltrisiloxane having one hydrogen atom bonded to the central silicon atom was used instead of hexadecamethyloctasiloxane. A polyether-modified siloxane compound 3 was obtained by the same method as in the synthesis example of the siloxane compound 1. As a result of structural analysis by NMR, the polyether-modified siloxane compound 3 was found to be a + b + c = 6, m = 0, n = 15, (a + b + c) / (n + m) = 0.4.

<Ink adjustment example>
(Example 1)
With the following formulation, ion-exchanged water was added so as to make a total of 100 parts by mass, and after the formulation, the mixture was mixed and stirred, and filtered through a 5 μm filter (Minisalt manufactured by Sartorius) to obtain the ink of Example 1.
・ Pigment dispersion: 15.0 parts by mass ・ Superflex 300 (polyurethane resin particles, resin solid content concentration: 30% by mass, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 26.7 parts by mass ・ Polyether-modified siloxane compound 1: 2.0 parts by mass ・ 1,2-propanediol: 10.0 parts by mass ・ 1,3-butanediol: 10.0 parts by mass ・ 3-methoxy-N, N-dimethylpropionamide: 8.0 parts by mass ・3-methoxy-3-methylbutanol: 5.0 parts by mass ・ Proxel LV (Abyssia preservative): 0.1 parts by mass ・ Ion exchange water: Remaining amount

(Examples 2 to 6, Comparative Examples 1 to 2)
The inks of Examples 2 to 6 and Comparative Examples 1 and 2 were prepared in the same manner as the inks of Example 1 with the formulations shown in Table 1. In Table 1, since each numerical value relating to the coloring material and the resin represents the total amount, the solid content amount relating to the coloring material and the resin is a value obtained by adding the solid content concentration to these numerical values. The unit of each numerical value is parts by mass, and the total amount of each ink is 100 parts by mass.

The following materials were used for each component in the table.
-WBR-2122C (polyurethane resin particles, resin solid content concentration: 30% by mass, manufactured by Taisei Fine Chemical Co., Ltd.)
-J-450 (styrene acrylic resin particles, resin solid content concentration: 42% by mass, manufactured by Johnson Polymer Co., Ltd.)

Using the obtained ink, "adhesion", "scratch resistance", "beading property", and "image glossiness" were evaluated as follows. The results are shown in Table 2.

[Formation of solid image]
The adjusted ink is filled in an inkjet printer (device name: IPSiO GXe5500 remodeling machine, manufactured by Ricoh Co., Ltd.), and the amount of ink adhered to the recording medium of PP film (Toyobo, P2161) is 0.6 g / cm ^2. As such, a solid image was recorded. After recording, the solid image was dried on a hot plate (NINOS ND-1, manufactured by AS ONE Corporation) at 80 ° C. for 1 hour.
The IPSiO GXe5500 remodeling machine is a remodeling of the IPSiO GXe5500 machine so that ^{a record equivalent to a recording speed of 30 m 2} / hr can be reproduced in A4 size with a printing width of 150 cm. The IPSiO GXe5500 remodeling machine is also equipped with the above hot plate, and is remodeled so that the heating conditions (heating temperature, heating time) after recording can be changed.

<Adhesion>
For the solid image formed on the recording medium of the PP film, the number of remaining squares of 100 test squares was counted by a grid peeling test using a cloth adhesive tape (manufactured by Nichiban Co., Ltd., 123LW-50). Based on the evaluation criteria, the "adhesion" to the recording medium was evaluated. It is desirable in actual use that the evaluation is B or higher.
〔Evaluation criteria〕
AA: Number of remaining cells is 98 or more A: Number of remaining cells is 90 or more and less than 98 B: Number of remaining cells is 70 or more and less than 90 C: Number of remaining cells is less than 70

<Scratch resistance>
In the formation of the solid image, the solid image was formed in the same manner except that a recording medium of PVC film (CPPVWP1300, manufactured by Sakurai Co., Ltd.) was used instead of the PP film. Next, this solid image was rubbed with a cotton cloth 10 times, and the degree of pigment transfer to the cotton cloth was visually observed and evaluated according to the following criteria. It is desirable that the evaluation is B or higher.
〔Evaluation criteria〕
A: Pigment transfer to cotton cloth is rarely seen B: Some pigment transfer is seen C: Pigment is clearly transferred

<Beading>
In the formation of the solid image, the solid image was formed in the same manner except that a recording medium of PVC film (CPPVWP1300, manufactured by Sakurai Co., Ltd.) was used instead of the PP film. Next, the recording unevenness of this solid image was visually observed, and the beading property was evaluated based on the following evaluation criteria. It is desirable in actual use that the evaluation is B or higher.
〔Evaluation criteria〕
A: Very good (no beading at all)
B: Good (slight beading was observed)
C: Normal (there was beading)
D: Defective (with significant beading)

<Image glossiness>
In the formation of the solid image, the solid image was formed in the same manner except that a recording medium of PVC film (CPPVWP1300, manufactured by Sakurai Co., Ltd.) was used instead of the PP film. Next, the 60 ° glossiness of this solid image was measured four times with a glossiness meter (manufactured by BYK Gardener, 4501), the average value of the gloss values was calculated, and the "image glossiness" was obtained based on the following evaluation criteria. Was evaluated. It is desirable that the evaluation is B or higher.
〔Evaluation criteria〕
AA: Gloss value is 100 or more A: Gloss value is 90 or more and less than 100 B: Gloss value is 80 or more and less than 90 C: Gloss value is less than 80

Examples 1 and 2 are preferable embodiments, and are excellent in adhesion and beading property, and high image glossiness can be obtained even when printed on a non-penetrating recording medium, and an image having scratch resistance can be obtained. You can see that it is done.
Example 3 is an example in which the resin solid content is 8.0% by mass or more, and the result is that the image glossiness is inferior to that of Examples 1 and 2.
Example 4 is an example not containing the compound represented by the general formula (2), and the beading property is inferior to that of Examples 1 and 2.
Example 5 is an example in which the amount of the polyether-modified siloxane compound added is slightly small, and the result is that the image glossiness is inferior to that of Examples 1 and 2.
Example 6 is an example in which the amount of the polyether-modified siloxane compound added is slightly large, resulting in inferior adhesion and beading property as compared with Examples 1 and 2.

Comparative Example 1 is an example in which the value of “(a + b + c) / (n + m)” of the polyether-modified siloxane compound is less than 0.5, resulting in inferior beading property and image glossiness as compared with Examples. ..
Comparative Example 2 is an example in which the urethane resin is not used, and the results show that the adhesion, scratch resistance, and image glossiness are inferior to those of the examples.

From the results in Table 2, it can be seen that the ink in this embodiment is suitable for outdoor use. In addition, the inks of Examples 1 to 6 were excellent in adhesion, scratch resistance, beading property, and image glossiness as compared with Comparative Examples.

400 Image forming device 401 Image forming device exterior 401c Device body cover 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y For each color of black (K), cyan (C), magenta (M), yellow (Y) Main tank 411 Ink storage unit 413 Ink discharge port 414 Storage container case 420 Mechanical unit 434 Discharge head 436 Supply tube

Japanese Unexamined Patent Publication No. 2017-115127

Claims (10)

An ink containing a polyether-modified siloxane compound represented by the following general formula (1), a urethane resin, and a coloring material.
(In the general formula (1), R represents a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms, and a, b, c, n, and m are (a + b + c) / (n + m) ≧ 0.5. Fulfill.) The ink according to claim 1, wherein the content of the urethane resin is 8.5% by mass or less with respect to the amount of the ink. The ink according to claim 1 or 2, which contains a compound represented by the following general formula (2).
(In the general formula (2), R ₁ , R ₂ , and R ₃ each independently represent a hydrocarbon group having 1 or more and 8 or less carbon atoms.) Any one of claims 1 to 3 in which the content of the polyether-modified siloxane compound represented by the general formula (1) is 1.0% by mass or more and 2.0% by mass or less with respect to the amount of the ink. The inks described in the section. An ink container containing the ink according to any one of claims 1 to 4. A recording device comprising the ink containing container according to claim 5 and an ink applying means for applying the contained ink to a recording medium. The recording device according to claim 6, wherein the ink applying means applies the ink to a non-permeable base material. A recording method comprising an ink applying step of applying the ink according to any one of claims 1 to 4. The recording device according to claim 8, wherein the ink application step applies the ink to a non-permeable substrate. A recording material having a recording medium and a printing layer formed on the recording medium and containing a polyether-modified siloxane compound represented by the following general formula (1), a urethane resin, and a coloring material.
(In the general formula (1), R represents a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms, and a, b, c, n, and m are (a + b + c) / (n + m) ≧ 0.5. Fulfill.)