JP2005344100A - New polymeric compound, composition containing the same, ink composition, inking method and inking device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a block polymeric compound enabling a functional substance to be dispersed homogeneously in a solvent, and to provide an ink composition using the compound. <P>SOLUTION: The block polymeric compound is an ABC triblock polymer composed of three kinds of block segments each constituted of a polyalkenyl ether main chain, wherein the A-segment is hydrophilic or hydrophobic, the B-segment is hydrophobic, and the C-segment is ionic. Either one of the above block segments has a block segment having recurring unit structures of the general formula(1) (wherein, R<SB>a</SB>, R<SB>b</SB>and R<SB>c</SB>are each H or CH<SB>3</SB>; and R<SP>1</SP>is a 1-18C straight-chain, branched or cyclic alkyl). The ink composition comprises the block polymeric compound, a solvent or dispersion medium and a coloring material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel polymer compound, a composition containing the same, an ink composition, an ink application method, and an ink application apparatus.

  For compositions containing granular solids, conventional functional materials such as herbicides, pesticides and other agricultural chemicals, anticancer agents, antiallergic agents, anti-allergic agents, and toners that use functional materials as coloring materials And ink are known. In recent years, digital printing technology has made great progress. Typical examples of the digital printing technology are electrophotographic technology and ink jet technology, but in recent years, the presence of image forming technology in offices, homes, and the like has been increasing.

  Among them, the ink jet technology has a great feature of compactness and low power consumption as a direct recording method. In addition, the image quality is rapidly increasing due to the miniaturization of nozzles. An example of the ink jet technology is a method in which ink supplied from an ink tank is heated by a heater in a nozzle to evaporate and foam, and the ink is ejected to form an image on a recording medium. Another example is a method of ejecting ink from a nozzle by vibrating a piezo element. With the development of these technologies, the image quality of digital color prints has improved remarkably and has reached a level that is not inferior to silver halide photography. Digital color prints are required to have weather resistance in addition to high image quality when used as an alternative to conventional silver halide photography and printing. In order to improve these, use of a pigment-dispersed ink (see Patent Document 1), laminating, and the like have been studied. However, many improvements are still desired.

Moreover, although the example using a polymer, for example, the polymer which has a sulfonic acid group is reported as a pigment dispersion method (refer patent document 2), there exists a point which should be improved by this. Furthermore, although an ink composition using an aqueous dispersion containing an ABC triblock polymer dispersant has also been reported (see Patent Document 3), fixing of the ink composition is due to penetration into paper, so as to improve printing speed. Therefore, further speeding up of fixing is desired.
US Pat. No. 5,085,698 US Pat. No. 5,713,993 US Pat. No. 5,519,085

The present invention has been made in view of such a background art, and provides a block polymer compound in which a functional substance is favorably dispersed in a solvent.
In addition, the present invention provides an ink composition in which the functional material is a color material and the solvent is preferably water, and the dispersibility of the color material is good.

The present invention also provides an ink composition having high color material dispersion stability in a solvent and further improved fixability.
The present invention also provides a liquid application method using the functional substance composition and a liquid application apparatus used therefor.

  The block polymer compound provided by the present invention is an ABC triblock polymer having three block segments composed of a polyalkenyl ether main chain, wherein the A segment of the block polymer is hydrophilic or hydrophobic, and B The segment is hydrophobic, the C segment is ionic, and at least one block segment of the block polymer has a block segment having a repeating unit structure represented by the following general formula (1) .

[Wherein, R _a , R _b and R _c are each independently H or CH ₃ . R ¹ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or — (CH (R ² ) —CH (R ³ ) —O) ₁ —R ⁴ or — (CH ₂ ) _m — ( O) selected from _n- R ⁴ . l and m are each independently selected from an integer of 1 to 12, and n is 0 or 1. R ² and R ³ are each independently H or CH ₃ . R ⁴ is H, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, —Ph, —Pyr, —Ph—Ph, —Ph—Pyr, —CHO, —CH ₂ CHO, —CO—CH. ═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ , —CH ₂ COOR ⁵ , —PhCOOR ⁵ , —CH ₂ SO ₃ R ⁵ , —PhSO ₃ R ⁵ , and R ⁴ is other than a hydrogen atom In this case, a hydrogen atom on the carbon atom can be substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, and a carbon atom in the aromatic ring can be substituted with a nitrogen atom. R ⁵ represents H, an alkyl group having 1 to 5 carbon atoms, or a monovalent to polyvalent cation. The present invention includes those in which the ionic C segment has at least one selected from carboxylic acid, carboxylate, sulfonic acid and sulfonate in its side chain.

Moreover, this invention includes the composition containing said ABC triblock polymer, a functional substance, and a solvent.
In the present invention, the solvent can be an aqueous solvent.

Moreover, a functional substance can be used as a color material. That is, the ink composition includes the ABC triblock polymer, the color material, and the solvent.
The ink application method provided by the present invention includes a step of preparing the ink composition of the present invention and a step of applying the ink composition to a medium.

  In addition, the ink applying device provided by the present invention includes an ink applying unit for applying energy to the ink composition of the present invention to apply ink to a medium, and a driving unit for driving the ink applying unit. It is characterized by having.

  According to the present invention, a block polymer compound in which a functional substance is favorably dispersed in a solvent can be provided. In addition, it is possible to provide an ink composition having high dispersion stability of the coloring material in the solvent and further improved fixing property. Further, an excellent ink application method and an ink application device can be provided by using the above-described composition having good dispersibility.

  The block polymer compound provided by the present invention is an ABC triblock polymer compound having three block segments composed of a polyalkenyl ether main chain, wherein the A segment of the block polymer is hydrophilic or hydrophobic, The B segment is hydrophobic, the C segment is ionic, and at least one block segment of the block polymer has a block segment having a repeating unit structure represented by the following general formula (1). To do.

[Wherein, R _a , R _b and R _c are each independently H or CH ₃ . R ¹ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or — (CH (R ² ) —CH (R ³ ) —O) ₁ —R ⁴ or — (CH ₂ ) _m — ( O) selected from _n- R ⁴ . l and m are each independently selected from an integer of 1 to 12, and n is 0 or 1. R ² and R ³ are each independently H or CH ₃ . R ⁴ is H, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, —Ph, —Pyr, —Ph—Ph, —Ph—Pyr, —CHO, —CH ₂ CHO, —CO—CH. ═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ , —CH ₂ COOR ⁵ , —PhCOOR ⁵ , —CH ₂ SO ₃ R ⁵ , —PhSO ₃ R ⁵ , and R ⁴ is other than a hydrogen atom In this case, a hydrogen atom on the carbon atom can be substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, and a carbon atom in the aromatic ring can be substituted with a nitrogen atom. R ⁵ represents H, an alkyl group having 1 to 5 carbon atoms, or a monovalent to polyvalent cation. ]

  In the present invention, the ionic C segment is a block polymer compound characterized in that it has at least one selected from carboxylic acid, carboxylate, sulfonic acid and sulfonate in its side chain. Is a preferred form.

More preferably, it is _a triblock polymer compound having a vinyl ether structure in which R _a , R _b , and R _c are H in the formula (1). More preferably, the ABC triblock polymer compound is a triblock polymer compound having stimulus responsiveness in at least one segment. More preferably, the number average molecular weight of the ABC triblock polymer is 8000 to 1,000,000, and the molecular weight distribution of the ABC triblock polymer is 1.8 or less. More preferably, the ABC triblock polymer has a glass transition temperature of 20 ° C. or lower.

  The present invention includes a functional substance composition containing the triblock polymer, a functional substance, and a solvent. More preferably, it is a functional substance composition comprising a triblock polymer, a coloring material, and a water-soluble solvent, and the functional substance is used as an ink composition with a coloring material, and the ink composition It is a preferred form that the product is used as an inkjet ink composition.

  The polymer of the present invention is a polymer having an ionic segment in the C segment. When the polymer of the present invention is used as a functional material composition containing a functional substance and an aqueous solvent, the ionic segment is dissociated. And can be dispersed in an aqueous solvent. In this case, it is also an embodiment of the present invention to use the solvent with alkalinity. Furthermore, when a color material is used as a functional substance and the ink composition is used as an ink jet ink composition, if the recording method is a thermal ink jet method, resistance in an alkaline environment at a high temperature is desired. In addition, the ionic segment in the C segment is polymerized while protecting with an appropriate protective group such as an ester group at the time of polymerization, and then the protective group is deprotected to form an ionic segment. Even in the case of using an alkali, the polymer is placed in an alkaline solution environment, and resistance at that time is desired.

The ink application method provided by the present invention includes a step of preparing the ink composition of the present invention and a step of applying the ink composition to a medium.
In addition, the ink applying device provided by the present invention includes an ink applying unit for applying energy to the ink composition of the present invention to apply ink to a medium, and a driving unit for driving the ink applying unit. It is characterized by having.

  The polyalkenyl structure that defines the block polymer compound of the present invention has an ether bond in the connection mode between the main chain and the side chain. On the other hand, the acrylic polymer is an ester. Therefore, when the polymer is in an alkaline state, particularly at a high temperature, there is a concern that the ester bond at the linking site may be hydrolyzed in the acrylic acid-based polymer. However, in the polymer of the present case, since the linkage mode is an ether bond, resistance in an alkaline state can be improved as compared with an ester bond.

A number of methods for synthesizing a polymer having a polyalkenyl ether structure have been reported (for example, JP-A-11-080221), but a method using cationic living polymerization by Aoshima et al. (JP-A-11-322942, JP-A-11-322866). Publication) is a typical example. Accurate length (molecular weight) of various polymers such as homopolymers, copolymers composed of two or more monomers, block polymers, graft polymers, gradient polymers, etc. It can be synthesized to match. Polyalkenyl ether can introduce various functional groups into its side chain. The cationic polymerization method can also be carried out by HI / I ₂ system, HCl / SnCl ₄ system or the like.

  In particular, the repeating unit structure of the alkenyl ether has the following general formula (1)

(However, R ¹ is as defined above.)
It is preferable that
In the present invention, a linear or branched alkyl group means methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, heptyl, octyl, nonyl, decyl. , Undecyl, dodecyl, octadecyl and the like. The cyclic alkyl group includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. When hydrogen on a carbon atom is substituted, the substitution may be at one location or multiple locations.

  Preferably, the vinyl ether polymer represented by the following general formula (2) is preferable as the repeating unit molecular structure of the polymer containing a polyalkenyl ether structure in the inkjet ink having the above-described stimulus responsiveness.

R ⁶ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, —Ph, —Pyr, —Ph—Ph, —Ph—Pyr, or — (CH ₂ —CH ₂ —O) _l. Selected from —R ⁷ or — (CH ₂ ) _m — (O) _n —R ⁷ , the hydrogen atom in the aromatic ring is a linear or branched alkyl group having 1 to 4 carbon atoms, and the carbon in the aromatic ring Each atom can be replaced with a nitrogen atom. l is selected from an integer of 1 to 18, m is selected from an integer of 1 to 36, and n is 0 or 1.

R ⁷ is H, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, —Ph, —Pyr, —Ph——Ph, —Ph—Pyr, —CHO, —CH ₂ CHO, — CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ , —CH ₂ COOR ⁸ , —PhCOOR ⁸ , —CH ₂ SO ₃ R ⁸ , —PhSO 3 R ⁸ , and when R ⁷ is other than a hydrogen atom, carbon A hydrogen atom on the atom can be substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, and a carbon atom in the aromatic ring can be substituted with a nitrogen atom. When R ⁷ is other than a hydrogen atom, the hydrogen atom on the carbon atom is a linear or branched alkyl group having 1 to 4 carbon atoms or F, Cl, Br, and the carbon atom in the aromatic ring is a nitrogen atom. , Hydrogen atoms can be substituted with F, Cl and Br, respectively. R ⁸ represents H, an alkyl group having 1 to 5 carbon atoms, or a monovalent to polyvalent cation.

Preferably, R ⁶ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, —Ph, —Ph—Ph, or — (CH ₂ —CH ₂ —O) 1 —R ⁷ or — (CH ₂ ) selected from _m- (O) _n -R ⁷ , the hydrogen atom in the aromatic ring is substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, and the carbon atom in the aromatic ring is substituted with a nitrogen atom, respectively. can do. l is selected from an integer of 1 to 18, m is selected from an integer of 1 to 36, and is 0 or 1. R ⁷ is H, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, —Ph, —Ph—Ph, —CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═ When CH ₇ , —CH ₂ COOR ⁸ , —PhCOOR ⁸ —CH ₂ SO ₃ R ⁸ , and —PhSO ₃ R ⁸ are used, and R ⁷ is other than hydrogen, the hydrogen atom on the carbon atom is from 1 carbon atom. 4 linear or branched alkyl groups or F, Cl, Br, and carbon atoms in the aromatic ring can be substituted with nitrogen atoms, and hydrogen atoms can be substituted with F, Cl, Br, respectively. R ⁸ represents H, an alkyl group having 1 to 5 carbon atoms, or a monovalent to polyvalent cation.

  More preferably, the structure of the alkenyl ether monomer is specified below as the repeating unit molecular structure of the polymer containing the polyalkenyl ether structure described above, but the polyalkenyl ether structure used in the present invention is not limited thereto.

  In the monomers (Ia to Iq) constituting the repeating unit represented by the general formula (1), the structures that can be polymers constituting the hydrophilic segment are Ia, If, I- h, Ij, and structures that can be a polymer constituting the hydrophobic segment are Id, Ie, Ii, I-1, Im, In, and Io.

  Moreover, it is a monomer that constitutes a stimulus-responsive segment, and a structure that can become a polymer that responds from heat to hydrophilicity to hydrophobicity or from hydrophobicity to hydrophilicity is Ib, Ic, or Ig. is there. Monomers constituting the ionic segment include Ik, Ip, and Iq, which are polymers that respond from pH to ions as a stimulus from hydrophilicity to hydrophobicity or from hydrophobicity to hydrophilicity. It is a possible structure.

  In addition, a monomer having a hydroxyl group, a carboxylic acid structure, or a sulfonic acid structure, such as Ia, Ij, Ik, Ip, Iq, or the like, has a protective group during polymerization, and has an alkylsilyl group ( For example, those protected with a t-butyldimethylsilyl group), an alkyl group (for example, ethyl ester) or the like are used.

Each block also includes a copolymer of an alkenyl ether monomer and another monomer.
The ratio of the A segment, the B segment, and the C segment contained in the block copolymer having a polyalkenyl ether structure in the present invention is 5 to 95 mol% for the A segment, 5 to 95 mol% for the B segment, and 2 to 2 for the C segment. It is preferable that it is 95 mol%, and the total of each segment is 100%. It is also appropriate to use stimulus-responsive segments. As an example, if it is (Ic), each segment has thermal responsiveness, and hydrophilicity and hydrophobicity can be controlled by temperature. If present, it can be used as a hydrophobic segment.

  A block polymer containing these alkenyl ether monomers and containing a polyalkenyl ether structure can be suitably used in the present invention. The polymer that can be used in the present invention is a polymer containing a polyalkenyl ether structure having stimuli responsiveness composed of the above alkenyl ether monomers, but is not limited thereto. Examples of these include those specified below, but the polymer used in the present invention is not limited thereto.

Here, b, g, and r in the structural formula represent the bonding mode in the copolymer, and mean block, gradient, and random, respectively.
Furthermore, it is preferable that the number of repeating units of the polyalkenyl ether (in the above (II-a) to (II-b), x, y, m, n) is independently 1 or more and 10,000 or less, Further, it is more preferable that the total (in the above (II-a) to (II-e), x + y + m + n) is 30 or more and 40,000 or less. When the B and C segments in the block polymer containing a polyalkenyl ether structure are each independently composed of two or more types of monomers, each segment may be a random polymer or a gradient polymer.

  Furthermore, the number average molecular weight of the triblock polymer is from 5,000 to 1,000,000, more preferably from 8,000 to 500,000. If the molecular weight is lower than this, the response to the stimulation of the triblock polymer and the desired function are impaired, and if the molecular weight is too large, the solubility in the solvent is impaired. This point is different from the typical molecular weight of 1000-7500 described in the above-mentioned US Pat. No. 5,519,085.

  The molecular weight distribution of the triblock polymer is advantageously smaller in order to develop the stimulus responsiveness of the triblock polymer, generally 1.8 or less, preferably 1.6 or less, More preferably, it is 1.3 or less. More preferably, it is 1.2 or less.

  Since the molecular structure becomes flexible by lowering the glass transition temperature and the affinity with the colorant is improved, the glass transition temperature of at least one segment of the triblock polymer is preferably 20 ° C. or lower, It is preferably 0 ° C. or lower, more preferably −20 ° C. or lower. Also from this point, it is a preferable form to use a polymer having an alkenyl ether structure.

  Further, the ink composition can have a response to stimulation. Due to the stimulus responsiveness, the ink characteristics are increased by giving a stimulus in the process of forming an image, thereby providing a good fixing property. As the stimulating species to be applied, an appropriate species is selected for forming an image from cations, temperature changes, exposure to electromagnetic waves, pH changes, density changes, and the like.

  The functional substance dispersion composition of the present invention can change its state (characteristic) in response to various stimuli. In the present invention, application of “stimulating” cations, change in temperature, application of electric field, exposure to light (electromagnetic waves) such as ultraviolet light, visible light or infrared light, change in pH of the composition, addition of chemical substances, and composition The density change of an object can be mentioned.

  As an example, when a polyvalent cation metal ion is imparted to a polymer having a carboxylic acid or sulfonic acid structure that is an anionic repeating unit structure in the side chain, an electric attractive force acts. Therefore, the functional material composition or the ink composition is thickened, and good fixability can be realized.

  In the present invention, in addition to the cation application described above, preferable stimuli include the following. The first is a temperature change, and the range of the temperature change is a range over the phase transition temperature of the composition. Second, it is exposure to electromagnetic waves, and the wavelength range of electromagnetic waves is preferably 100 to 800 nm. Third, it is the pH change of the composition, and the range of the pH change is preferably in the range of pH 3 to pH 12. Fourth, a change in the concentration of the composition, for example, by changing the concentration of the composition by evaporating or absorbing the solvent of the composition or by changing the concentration of the dissolved polymer in the composition. The case where it does is mentioned. The change in the concentration is preferably in a range before and after the concentration at which the composition causes a phase transition. In the present invention, two or more kinds of stimuli may be applied in combination.

  Examples of the state change in response to the stimulus in the present invention include a phase change from a sol state to a gel state, a phase change from a solution state to a solid state, and a chemical structure change. In addition, “stimulus responsiveness” in the present invention means that the composition of the present invention changes its properties in response to the above-described stimulation. In other words, the stimulus responsiveness refers to this stimulus (environment) by applying stimuli such as temperature change, electric field application, exposure to electromagnetic waves, pH change, addition of chemical substances, and composition concentration change to the composition. It means that the shape and physical properties of the composition change remarkably according to (change).

  This characteristic can be used to improve the fixing speed when the ABC triblock polymer is used as an ink composition, for example. That is, by applying a stimulus after recording or printing on paper as a non-recording medium, the ink composition is thickened, and bleeding can be prevented, double-sided printing, and high-speed speed can be improved. This is also a feature of the present case that differs from the above-mentioned US Pat. No. 5,519,085 that uses only the permeability of ink to paper for fixing. Further, when the ABC triblock polymer is used as, for example, an ink composition, the scratch resistance can be improved. As will be described in detail later, the ABC triblock polymer has a micelle forming ability, and it is also a preferred form to be used as an ink in a form including a coloring material. By including the color material, even if the ink is applied to the recording medium and then rubbed with a line marker or the like, the color material is not directly touched. This is also a feature of the present invention which is different from the invention disclosed in US Pat. No. 5,519,085.

The present invention includes a functional substance composition containing the triblock polymer, a functional substance, and a solvent.
The content of the block polymer contained in the ink composition of the present invention is 0.1 to 50% by mass, preferably 0.5 to 30% by mass. When the amount of the block polymer is less than 0.1% by mass, the coloring material contained in the ink composition of the present invention may not be sufficiently dispersed. When the amount exceeds 50% by mass, the viscosity becomes too large. There is.

A preferred embodiment of the present invention is a functional material-dispersed composition in which a substance and a block polymer are dispersed in a solvent as particles, but is not limited thereto.
[water]
The water contained in the inkjet ink of the present invention is preferably ion-exchanged water, pure water, or ultrapure water from which metal ions or the like have been removed.

[Aqueous solvent]
Examples of the aqueous solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin and other polyhydric alcohols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol. Polyhydric alcohol ethers such as monoethyl ether and diethylene glycol monobutyl ether, nitrogen-containing solvents such as N-methyl-2-pyrrolidone, substituted pyrrolidone, and triethanolamine can be used. In addition, monohydric alcohols such as methanol, ethanol, and isopropyl alcohol can be used for the purpose of accelerating the drying of the inkjet ink on the recording medium.

  In the present invention, the content of the water and the aqueous solvent is preferably in the range of 20 to 95% by mass with respect to the total weight of the inkjet ink. More preferably, it is the range of 30-95 mass%.

[Color material]
The color material useful in the present invention may be a liquid or solid color material, or a solid dye dissolved in a solvent, depending on the use of the ink-jet ink of the present invention. good.

  The pigment may be either an organic pigment or an inorganic pigment, and the pigment used in the ink is preferably a black pigment and primary color pigments of cyan, magenta, yellow, red, green and blue. Color pigments other than those described above, colorless or light color pigments, metallic luster pigments, and the like may be used. In addition, a newly synthesized pigment may be used for the present invention. The pigment used preferably has an average primary particle diameter of 50 nm, and a commercially available pigment can also be used. However, the pigment is classified into fine particles (for example, mechanical crushing by milling). It is also possible to use it.

Examples of commercially available pigments for black, cyan, magenta, and yellow are shown below. Examples of black pigments include Raven 1060, Raven 1080, Raven 1170, Raven 1200, Raven 1250, Raven 1255, Raven 1500, Raven 2000, Raven 3500, Raven 5250, Raven 5750, Raven 5000, Raven 5000.
ULTRAII, Raven1190 ULTRAII (manufactured by Columbian Carbon), Black Pearls L, MOGUL-L, Regal400R, Regal660R, Regal330R, Monarch 800, Monarch 880, Monarch 900, 300, Monarch 1000, Monch 1000, Mon , Color Black FW1, Color Black FW200, Color Black FW200, Color Black 18, Color Black S160, Color Black S170, Special Black 4P, Special BlackP rintex140U, PrintexV, (all manufactured by Degussa) Printex140V, No. 25, no. 33, no. 40, no. 47, no. 52, no. 900, no. 2300, MCF-88, MA600, MA7, MA8, MA100 (manufactured by Mitsubishi Chemical Co., Ltd.) and the like can be mentioned, but are not limited thereto.

  Examples of cyan pigments include C.I. I. Pigment Blue-1, C.I. I. Pigment Blue-2, C.I. I. Pigment Blue-3, C.I. I. Pigment Blue-15, C.I. I. Pigment Blue-15: 2, C.I. I. Pigment Blue-15: 3, C.I. I. Pigment Blue-15: 4, C.I. I. Pigment Blue-16, C.I. I. Pigment Blue-22, C.I. I. Pigment Blue-60 etc. are mentioned, but it is not limited to these.

  Examples of magenta pigments include C.I. I. Pigment Red-5, C.I. I. Pigment Red-7, C.I. I. Pigment Red-12, C.I. I. Pigment Red-48, C.I. I. Pigment Red-48: 1, C.I. I. Pigment Red-57, C.I. I. Pigment Red-112, C.I. I. Pigment Red-122, C.I. I. Pigment Red-123, C.I. I. Pigment Red-146, C.I. I. Pigment Red-168, C.I. I. Pigment Red-184, C.I. I. Pigment Red-202, C.I. I. Pigment Red-207 and the like, but are not limited thereto.

  Examples of yellow pigments include C.I. I. Pigment Yellow-12, C.I. I. Pigment Yellow-13, C.I. I. Pigment Yellow-14, C.I. I. Pigment Yellow-16, C.I. I. Pigment Yellow-17, C.I. I. Pigment Yellow-74, C.I. I. Pigment Yellow-83, C.I. I. Pigment Yellow-93, C.I. I. Pigment Yellow-95, C.I. I. Pigment Yellow-97, C.I. I. Pigment Yellow-98, C.I. I. Pigment Yellow-114, C.I. I. Pigment Yellow-128, C.I. I. Pigment Yellow-129, C.I. I. Pigment Yellow-151, C.I. I. Pigment Yellow-154 and the like, but are not limited thereto.

  The pigment used in the ink of the present invention is preferably 0.1 to 50% by mass with respect to the weight of the ink. When the amount of the pigment is less than 0.1% by mass, a sufficient image density cannot be obtained, and when it exceeds 50% by mass, the fixability of the image may be deteriorated. A more preferable range is from 0.5% by mass to 30% by mass.

  In the case of a dye used by dissolving in a solvent, a water-soluble dye or a fat-soluble dye can be appropriately used. The coloring material used in the ink dispersion of the present invention is preferably 0.1 to 50% by mass with respect to the weight of the aqueous composition. The dye that can be used in the inkjet ink of the present invention may be a known dye, such as a direct dye, an acidic dye, a basic dye, a reactive dye, a water-soluble dye for food coloring, or a fat-soluble dye as described below. Dyes can be used.

Specific examples of the dye when using the inkjet ink of the present invention are shown below.
For example, water-soluble dyes include C.I. I. Direct black, -17, -19, -22, -32, -38, -51, -62, -71, -108, -146, -154;
C. I. Direct yellow, -12, -24, -26, -44, -86, -87, -98, -100, -130, -142;
C. I. Direct red, -1, -4, -13, -17, -23, -28, 31, -62, -79, -81, -83, -89, -227, -240, -242, -243 ;
C. I. Direct blue, -6, -22, -25, -71, -78, -86, -90, -106, -199;
C. I. Direct orange, −34, −39, −44, −46, −60;
C. I. Direct violet, -47, -48;
C. I. Direct brown, -109;
C. I. Direct green, direct dyes such as -59,
C. I. Acid Black, −2, −7, −24, −26, −31, −52, −63, −112, −118, −168, −172, −208;
C. I. Acid Yellow, -11, -17, -23, -25, -29, -42, -49, -61, -71;
C. I. Acid Red, -1, -6, -8, -32, -37, -51, -52, -80, -85, -87, -92, -94, -115, -180, -254, -256 , -289, -315, -317;
C. I. Acid Blue, −9, −22, −40, −59, −93, −102, −104, −113, −117, −120, −167, −229, −234, −254;
C. I. Acid Orange, -7, -19;
C. I. Acid violet, acid dyes such as -49,
C. I. Reactive Black, -1, -5, -8, -13, -14, -23, 31, 34, -39;
C. I. Reactive Yellow, -2, -3, -13, -15, -17, -18, -23, -24, -37, -42, -57, -58, -64, -75, -76,- 77, -79, -81, -84, -85, -87, -88, -91, -92, -93, -95, -102, -111, -115, -116, -130, -131, -132, -133, -135, -137, -139, -140, -142, -143, -144, -145, -146, -147, -148, -151, -162, -163;
C. I. Reactive Red, -3, -13, -16, -21, -22, -23, -24, -29, 31, 333, 35, 455, -49, -55, -63,- 85, -106, -109, -111, -112, -113, -114, -118, -126, -128, -130, -131, -141, -151, -170, -171, -174, -176, -177, -183, -184, -186, -187, -188, -190, -193, -194, -195, -196, -200, -201, -202, -204, -206 , -218, -221;
C. I. Reactive blue, -2, -3, -5, -8, -10, -13, -14, -15, -18, -19, -21, -25, -27, -28, -38,- 39, −40, −41, −49, −52, −63, −71, −72, −74, −75, −77, −78, −79, −89, −100, −101, −104, -105, -119, -122, -147, -158, -160, -162, -166, -169, -170, -171, -172, -173, -174, -176, -179, -184 , -190, -191, -194, -195, -198, -204, -211, -216, -217;
C. I. Reactive orange, -5, -7, -11, -12, -13, -15, -16, -35, -45, -46, -56, -62, -70, -72, -74,- 82, -84, -87, -91, -92, -93, -95, -97, -99;
C. I. Reactive violet, -1, -4, -5, -6, -22, -24, -33, -36, -38;
C. I. Reactive Green, -5, -8, -12, -15, -19, -23;
C. I. Reactive dyes such as reactive brown, -2, -7, -8, -9, -11, -16, -17, -18, -21, -24, -26, 31, -32, -33;
C. I. Basic black, -2;
C. I. Basic Red, -1, -2, -9, -12, -13, -14, -27;
C. I. Basic blue, -1, -3, -5, -7, -9, -24, -25, -26, -28, -29;
C. I. Basic violet, -7, -14, -27;
C. I. Food black, -1, -2, etc. are mentioned.

  Examples of the fat-soluble dyes include Oil Orange 201, Oil Orange PR, Oil Brown BB, Oil Brown GR, Oil Brown 416, Oil Green 502, VALIFAST GREEN 150G, VALIFAST GREEN 25Gil Y2G 860, Oil Black BS, Oil Black HBB, Oil Black BY, and the like.

  These examples of the liquid color material are particularly preferable for the ink-jet ink of the present invention, but the liquid color material used for the ink-jet ink of the present invention is particularly limited to the color material. is not.

  The liquid color material used in the inkjet ink of the present invention is preferably 0.1 to 50% by mass with respect to the weight of the ink. When the amount of the dye is less than 0.1% by mass, a sufficient image density cannot be obtained, and when it exceeds 50% by mass, the fixability of the image may be deteriorated. A more preferable range is from 0.5% by mass to 30% by mass.

[Additive]
Various additives, auxiliaries and the like can be added to the inkjet ink of the present invention as necessary.

  One additive for inkjet ink is a dispersion stabilizer that stably disperses polymer micelles in a solvent. The ink-jet ink of the present invention has a function of stabilizing the dispersion with a polymer containing a polyalkenyl ether structure. However, if the dispersion is insufficient, another dispersion stabilizer may be added.

As another dispersion stabilizer, it is possible to use a resin or a surfactant having both hydrophilic and hydrophobic portions.
Examples of the resin having both hydrophilic and hydrophobic parts include a copolymer of a hydrophilic monomer and a hydrophobic monomer. Hydrophilic monomers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, or the above carboxylic acid monoesters, vinyl sulfonic acid, styrene sulfonic acid, vinyl alcohol, acrylamide, methacryloxyethyl phosphate, etc. Styrene derivatives such as styrene and α-methylstyrene, vinylcyclohexane, vinylnaphthalene derivatives, acrylic acid esters, and methacrylic acid esters. Copolymers having various configurations such as random, block, and graft copolymers can be used. Of course, both hydrophilic and hydrophobic monomers are not limited to those shown above.

As the surfactant, an anionic, nonionic, cationic or amphoteric surfactant can be used.
Examples of anionic active agents include fatty acid salts, alkyl sulfate esters, alkylaryl sulfonates, alkyl diaryl ether disulfonates, dialkyl sulfosuccinates, alkyl phosphates, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyls. Examples thereof include phosphate ester salts and glycerol borate fatty acid esters.

  Nonionic activators include polyoxyethylene alkyl ethers, polyoxyethyleneoxypropylene block copolymers, sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based, silicon-based and the like. It is done.

Examples of the cationic activator include alkylamine salts, quaternary ammonium salts, alkylpyridinium salts, alkylimidazolium salts and the like.
Examples of amphoteric activators include alkylbetaines, alkylamine oxides, phosphadylcholines, and the like. Similarly, the surfactant is not limited to the above.

  Furthermore, an aqueous solvent can be added to the inkjet ink of the present invention as necessary. In particular, when used in an inkjet ink, the aqueous solvent is used to prevent drying at the nozzle portion of the ink and solidification of the ink, and can be used alone or in combination. As the aqueous solvent, those described above are applied as they are. In the case of ink, the content is 0.1 to 60% by mass, preferably 1 to 25% by mass, based on the total weight of the ink.

  Other additives include pH adjusters to stabilize ink jet ink and ink jet ink piping in the recording device, accelerate ink penetration into the recording medium, and speed up apparent drying. Chelating agent that prevents the generation of wrinkles in the ink, the antifungal agent that prevents the generation of wrinkles in the ink, and the metal ions in the ink, thereby preventing the deposition of metal at the nozzle or the insoluble matter in the ink. Anti-foaming agent, antioxidant, anti-fungal agent, viscosity modifier, conductive agent, ultraviolet absorber, and water-soluble dye, which prevents the generation of bubbles during the production, recording liquid circulation, movement Disperse dyes, oil-soluble dyes, and the like can also be added.

The specific contents of the inkjet ink (aqueous dispersion ink), which is a preferred embodiment of the ink of the present invention, are described below.
[Inkjet ink creation method]
Regarding the ink production method, as a preferred embodiment of the color material and the triblock polymer, the ink is prepared by first dispersing or dissolving the color material with a solvent, and then dissolving this solution in an aqueous solution in which the triblock polymer is dispersed or dissolved. Although the manufacturing process to disperse | distribute is mention | raise | lifted by adding and then removing an organic solvent, the manufacturing process in this invention is not limited to this.

  An example of dispersing the triblock polymer is dispersion using a disperser, for example, an ultrasonic homogenizer, a laboratory homogenizer, a colloid mill, a jet mill, a ball mill, etc., and these may be used alone or in combination. .

  Further, the triblock polymer can be appropriately used in an ink composition containing a coloring material. Even if this polymer does not contain a functional substance such as a color material, the lyophobic segments aggregate in a solvent, and the surroundings are solvated and covered with the new medium segments to form an aggregate.

  Amphiphilic block polymers are known to have various self-assembled forms in solution. Depending on the hydrophilic segment of the amphiphilic polymer, the ratio of the hydrophobic segment, the concentration of the solution, etc. Have a different form. The inclusion described in the present invention is due to micelle formation of an amphiphilic block polymer. An example of using water as a solvent will be described. In the aqueous solution, hydrophobic segments gather together, and a hydrophilic segment covers the periphery and disperses in water. At this time, if a water-insoluble colorant and a hydrophobic polymer are present in the solution, the hydrophobic substance is taken into the hydrophobic segment portion of the amphiphilic block polymer and is included in the micelle.

  Confirmation of micelle formation can be performed by observing this ink composition by cryo-transfer EF-TEM to observe spherical micelles. Moreover, it can confirm that it is included by conducting an elemental analysis of this sample by EELS. It is also possible to check the encapsulated state using the stimulus responsiveness of the ink composition. Description will be made using ABC triblock block polymer (II-d), which is an amphiphilic block polymer exemplified as an example, and a pigment as a coloring material. The ABC triblock block polymer (II-d) has an alkaline pH and ionizes the C segment. At 20 ° C or lower, the A segment responds to a stimulus and becomes fresh water. That is, in an acidic environment of 20 ° C. or higher, the ABC triblock polymer (II-d) is all hydrophobic in each segment, has no micelle forming ability, and precipitates in an aqueous solvent. As a result, the pigment and the hydrophobic polymer are in direct contact with the solvent without being encapsulated and cannot be dispersed or dissolved by themselves, so that phase separation and precipitation can be confirmed, and the aqueous phase is completely decolorized. This also shows that it was included in the amphiphilic block polymer micelle.

  In the examples to be described later, regarding the ink composition when the solvent is an aqueous solvent and the pigment is used as a functional substance, the triblock polymer forms micelles by enclosing a coloring material. This feature is different from the invention described in US Pat. No. 5,519,085.

[Ink application method and ink application apparatus]
The ink in the present invention can be used in various ink application devices such as various printing methods, ink jet methods, and electrophotographic methods, and can be drawn by an ink application method using this device.

  In the present invention, for example, as an inkjet printer using an inkjet ink, various inkjet recording apparatuses such as a piezo inkjet system using a piezoelectric element and a thermal inkjet system that performs recording by foaming ink by applying thermal energy. There is.

  In the apparatus of the present invention, for example, in the case of inkjet ink, the amount of ink ejected from the ejection port of the ejection head may be in the range of 0.1 picoliter to 100 picoliter in order to improve the image resolution. preferable.

  In particular, in the case of an ink jet recording apparatus, as one aspect thereof, the recording apparatus of the present invention includes an ink jet ink and an additive (crosslinking agent) that crosslinks the block polymer as a composition that gives a stimulus for changing the solvent environment. A means for contacting with the composition containing. In this aspect, the ink-jet ink is fixed on the recording medium by this contact, and an excellent image is formed.

  The ink-jet ink of the present invention can also be used in an indirect recording apparatus using a recording method in which ink is printed on an intermediate transfer member and then transferred to a recording medium such as paper. Also, the present invention can be applied to an apparatus using an intermediate transfer member by a direct recording method.

  In particular, the ink-jet ink of the present invention can be used in an electrophotographic recording type image forming method and an image forming apparatus. For example, the image forming apparatus includes a photosensitive drum for forming a latent image, and includes a means (such as an exposure device) for forming a latent image on the photosensitive drum, an ink applying unit, a transfer mechanism, and a recording medium. Things can be mentioned. In the image formation by this apparatus, first, a latent image is formed on the photosensitive drum, the ink jet ink of the present invention is applied to the latent image or a portion other than the latent image, and the obtained image is transferred to a recording medium by a transfer mechanism. Transfer and fix.

An outline of the ink jet recording apparatus will be described below with reference to FIG. However, FIG. 1 is merely an example of the configuration and does not limit the present invention.
FIG. 1 is a block diagram showing the configuration of the ink jet recording apparatus.

  FIG. 1 shows a case where recording is performed on a recording medium by moving the head. In FIG. 1, an X direction drive motor 56 and a Y direction drive motor 58 for driving the head 70 in the XY directions include an X motor drive circuit 52 and a Y motor drive circuit 54 for the CPU 50 that controls the overall operation of the manufacturing apparatus. Connected through. In accordance with an instruction from the CPU, the X direction drive motor 56 and the Y direction drive motor 58 are driven through the X motor drive circuit 52 and the Y motor drive circuit 54, and the position of the head 70 with respect to the recording medium is determined.

  As shown in FIG. 1, a head drive circuit 60 is connected to the head 70 in addition to the head 70 in addition to the X direction drive motor 56 and the Y direction drive motor 58, and the CPU 50 controls the head drive circuit 60. The head 70 is driven, that is, ink jet ink is discharged. Further, an X encoder 62 and a Y encoder 64 for detecting the head position are connected to the CPU 50, and position information of the head 70 is input. A control program is also input into the program memory 66. The CPU 50 moves the head 70 based on this control program and the positional information of the X encoder 62 and the Y encoder 64, disposes the head at a desired position on the recording medium, and ejects ink for inkjet. In this way, desired drawing can be performed on the recording medium. Further, in the case of an image recording apparatus capable of loading a plurality of ink jet inks, desired drawing can be performed on a recording medium by performing the above-described operation for each ink jet ink a predetermined number of times.

  In addition, after ejecting the ink jet ink, the head 70 is moved to a position where removing means (not shown) for removing excess ink adhering to the head is arranged, if necessary. It can also be cleaned by wiping or the like. As a specific method of cleaning, a conventional method can be used as it is.

When drawing is completed, the drawn recording medium is replaced with a new recording medium by a recording medium conveyance mechanism (not shown).
Note that the present invention can be modified or modified without departing from the gist of the present invention. For example, in the above description, the example in which the head 70 is moved in the XY axis direction has been shown, but the head 70 is moved only in the X axis direction (or Y axis direction), and the recording medium is moved in the Y axis direction (or X axis). The image may be drawn while moving in the axial direction) and interlocking with each other.

  The present invention includes means for generating thermal energy (for example, an electrothermal converter, a laser beam, etc.) as an energy source used for ejecting inkjet ink, and ejects inkjet ink by the thermal energy. The head has an excellent effect. According to this method, high definition of drawing can be achieved. By using the ink-jet ink of the present invention, further excellent drawing can be performed.

  As for the typical configuration and principle of the apparatus provided with the means for generating the heat energy, for example, the basic principle disclosed in US Pat. Nos. 4,723,129 and 4,740,796 is used. What to do is preferred. This method can be applied to both the so-called on-demand type and the continuous type. In particular, in the case of the on-demand type, the liquid is retained and electrothermal conversion is arranged corresponding to the flow path. By applying to the body at least one drive signal corresponding to the ejection information and providing a rapid temperature rise exceeding the nucleate boiling, heat energy is generated in the electrothermal transducer, and film boiling occurs on the heat acting surface of the head. As a result, bubbles in the liquid corresponding to the drive signal on a one-to-one basis can be formed, which is effective. By the growth and contraction of the bubbles, the liquid is discharged through the discharge opening to form at least one droplet. It is more preferable that the drive signal has a pulse shape, since the bubble growth and contraction is performed immediately and appropriately, and thus it is possible to achieve liquid discharge with particularly excellent responsiveness. As this pulse-shaped drive signal, those described in US Pat. Nos. 4,463,359 and 4,345,262 are suitable. In addition, when the conditions described in US Pat. No. 4,313,124 of the invention relating to the temperature increase rate of the heat acting surface are adopted, further excellent discharge can be performed.

  As the configuration of the head, in addition to the combination configuration (straight liquid channel or right-angle liquid channel) of the discharge port, the liquid channel, and the electrothermal transducer as disclosed in each of the above-mentioned specifications, Configurations using US Pat. No. 4,558,333 and US Pat. No. 4,459,600, which disclose configurations disposed in the bending region, are also included in the present invention. In addition, for a plurality of electrothermal transducers, Japanese Patent Application Laid-Open No. 59-123670 that discloses a configuration in which a common slit is used as a discharge portion of the electrothermal transducer, or an aperture that absorbs pressure waves of thermal energy is provided. The effect of the present invention is also effective as a configuration based on Japanese Patent Application Laid-Open No. 59-138461 which discloses a configuration corresponding to the discharge unit. In other words, regardless of the form of the head, according to the present invention, it is possible to reliably and efficiently discharge ink jet ink.

  Further, the present invention can be effectively applied to a full-line type head having a length corresponding to the maximum width of a recording medium in the image forming apparatus of the present invention. As such a head, either a configuration satisfying the length by a combination of a plurality of heads or a configuration as a single head integrally formed may be used.

  In addition, a serial type head that is fixed to the main body of the apparatus or mounted on the main body of the apparatus can be electrically connected to the main body of the apparatus and ink can be supplied from the main body. The present invention is also effective when a chip-type head is used.

Furthermore, the apparatus of the present invention may further include a droplet removing unit. When such means is provided, a further excellent discharge effect can be realized.
In addition, it is preferable to add preliminary auxiliary means or the like as the configuration of the apparatus of the present invention because the effects of the present invention can be further stabilized. Specifically, a capping unit for the head, a pressurizing or sucking unit, an electrothermal converter or a heating element different from this, or a preheating unit for heating using a combination thereof, A preliminary ejection means for performing ejection other than the ejection of ink can be used.

  The most effective method for the present invention employs the film boiling method described above.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In the following examples, a method for synthesizing the triblock polymer of the present invention and an inkjet ink will be described by taking disperse dye inkjet ink as an example. In the examples of these polymer synthesis and disperse dye inks, only a few specific examples are shown, but the present invention is not limited thereto.

Example 1
<Synthesis of ABC triblock polymer: methoxyethyl alkenyl ether (MOVE) as A segment, isobutyl alkenyl ether and CH ₂ = CHOCH ₂ CH ₂ OPhPh as B segment, random copolymer (IBVE-r-BPhOVE), C Synthesis of a triblock polymer composed of 4- (2-vinyloxy) ethoxybenzoic acid (HBVE) as a segment, poly [MOVE-b- (IBVE-r-BPhOVE) -b-HBVE] (II-f)> (here , B is a block polymer, and r is a random polymer symbol)

  After the inside of the glass container fitted with the three-way cock was replaced with nitrogen, the adsorbed water was removed by heating to 250 ° C. in a nitrogen gas atmosphere. After returning the system to room temperature, 20 mmol (Mole) of MOVE, 16 mmol of ethyl acetate, 0.1 mmol of 1-isobutoxyethyl acetate, and 11 ml of toluene were added, and the reaction system was cooled. When the system temperature reached 0 ° C., 0.2 mmol of ethylaluminum sesquichloride (an equimolar mixture of diethylaluminum chloride and ethylaluminum dichloride) was added to initiate polymerization. The molecular weight was monitored in a time-sharing manner using molecular sieve column chromatography (GPC) and NMR to confirm the completion of polymerization of the A block.

  Next, 5 mmol each of BPhOVE 5 mmol and IBVE were added as B block components, and polymerization was continued. The molecular weight was monitored in a time-sharing manner using molecular sieve column chromatography (GPC) and NMR to confirm the completion of polymerization of the B block and the formation of the AB diblock polymer.

  Subsequently, a toluene solution of 9 mmol ethyl 4- (2-vinyloxy) ethoxybenzoate was added to continue the polymerization. After 24 hours, the polymerization reaction was stopped. The polymerization reaction was stopped by adding a 0.3% by mass ammonia / methanol aqueous solution to the system. The reaction mixture solution was diluted with dichloromethane, washed 3 times with 0.6 mol / L hydrochloric acid and then 3 times with distilled water, and the organic phase obtained was concentrated and dried to dryness with an evaporator. Then, dialysis in a methanol solvent was repeated using a semipermeable membrane of cellulose to remove the monomeric compound to obtain a target triblock polymer. The compound was identified using NMR and GPC. Mn = 24500 and Mw / Mn = 1.29. The polymerization ratio was A: B: C = 190: 100: 30. The polymerization ratio of the two monomers in the B block was 1: 1.

  Furthermore, by hydrolyzing the trilock polymer obtained here in a mixed solution of dimethylformamide and aqueous sodium hydroxide, ethyl 4- (2-vinyloxy) ethoxybenzoate in the C block component is hydrolyzed, and sodium A chlorinated triblock polymer, that is, a triblock polymer having a repeating unit structure in which the C segment is a hydrophilic block segment and is anionic was obtained. The compound was identified using NMR and GPC.

  Further, a triblock polymer, poly [MOVE-b- (IBVE), in which 4- (2-vinyloxy) ethoxybenzoic acid in component C is converted to a free carboxylic acid by neutralization with 0.1N hydrochloric acid in an aqueous dispersion. -R-BPhOVE) -b-HBVE]. The compound was identified using NMR and GPC.

Example 2
13 parts by weight of the above trilock polymer and 5 parts by weight of a fat-soluble dye oil blue N (same as the trade name, manufactured by Aldrich) are co-dissolved in dimethylformamide and converted into an aqueous phase using 400 parts by weight of distilled water. An ink composition was obtained. 0.1 ml of 0.1N sodium hydroxide aqueous solution was added thereto, and the mixture was allowed to stand for 1 hour in an ultrasonic homogenizer over 10 minutes. The pH test paper had a pH of 12. This dispersion was very clear and had a blue color. Although left for 10 days, the fat-soluble dye did not separate and precipitate.

  Further, as described above, the inclusion of the coloring material and the hydrophobic polymer was confirmed using EF-TEM observation by cryotransfer, elemental analysis by EELS, and stimulation responsiveness of the ABC block polymer in the coloring material dispersion.

  The ink composition obtained above was filled in a print head of an ink jet printer (BJF800, manufactured by Canon Inc.) and discharged onto a recording medium to obtain an image. As the recording medium, plain paper sprayed with hydrochloric acid was used, and a recording medium capable of giving stimulation was prepared. The recording medium and the dispersion composition were evaluated using the following methods (1) to (2).

  (1) A 50 mm × 50 mm square was printed with the above printer, and when the recording part was strongly pressed with the finger 30 seconds after printing, the ink did not adhere to the finger. This is thought to be because the triblock polymer in the ink composition increased in viscosity after printing, and the fixing speed was increased, and in addition, the triblock polymer contained a coloring material, and thus the scratch resistance was improved. It is done.

  (2) A 50 mm × 50 mm square was printed with the printer using a solid, and after 30 seconds of printing, the image was rubbed with a line marker 5 times, and blue tailing was not observed. This is thought to be because the triblock polymer in the ink composition increased in viscosity after printing, and the fixing speed was increased, and in addition, the triblock polymer contained a coloring material, and thus the scratch resistance was improved. It is done.

Comparative Example 1
Water-soluble dyes C.I. I. By stirring 4 parts by weight of Direct Blue-199 and 17 parts by weight of diethylene glycol in 79 parts by weight of distilled water, a water-soluble dye ink having a very clear blue color was obtained. As the recording medium, plain paper sprayed with hydrochloric acid prepared in Example 2 and plain paper not sprayed were used. Evaluation was performed in the same manner as in Example 2.

  (1) A square of 50 mm × 50 mm was printed with the above printer with a solid, and the recording part was strongly pressed with a finger 30 seconds after printing. In both cases where the plain paper sprayed with hydrochloric acid and the plain paper not sprayed were used as the recording medium, the ink adhered to the finger.

  (2) A 50 mm × 50 mm square was printed with the printer using a solid, and after 30 seconds of printing, the image was strongly rubbed once with a line marker. When the plain paper sprayed with hydrochloric acid and the plain paper not sprayed were used as the recording medium, blue bleeding was observed.

Example 3
<2-methoxyethyl vinyl ether: and (MOVE A block), isobutyl vinyl ether and CH ₂ = CHOCH ₂ CH ₂ OPhPh random copolymer of: a: (IBVE-r-VEEtPhPH B block), 4- (2-vinyloxy) Synthesis of triblock polymer consisting of methyl ethoxy-benzenesulfonate (VEOEtPhSO ₃ Me: C block). >

  After the inside of the glass container fitted with the three-way cock was replaced with nitrogen, the adsorbed water was removed by heating to 250 ° C. in a nitrogen gas atmosphere. After returning the system to room temperature, MOVE 24 mmol (mmol), ethyl acetate 16 mmol, 1-isobutoxyethyl acetate 0.1 mmol, and toluene 11 ml were added, and the reaction system was cooled. When the system temperature reached 0 ° C., 0.2 mmol of ethylaluminum sesquichloride (an equimolar mixture of diethylaluminum chloride and ethylaronium dichloride) was added to initiate polymerization. The molecular weight was monitored in a time-sharing manner using molecular sieve column chromatography (GPC) to confirm the completion of polymerization of the A block.

  Next, 6 mmol (mmol) of IBVE of B block and 6 mmol of toluene solution of VEEtPhPh were added, and polymerization was continued. After the completion of polymerization of the B block was confirmed by monitoring using GPC, 12 mmol of a toluene solution of the C block component was added, and the polymerization was continued. After 24 hours, the polymerization reaction was stopped.

  The polymerization reaction was stopped by adding a 0.3% by mass ammonia / methanol aqueous solution to the system. The reaction mixture solution was diluted with dichloromethane and washed 3 times with 0.6M hydrochloric acid and then 3 times with distilled water. The organic phase obtained was concentrated and dried with an evaporator, and then vacuum-dried, and then repeatedly dialyzed in a methanol solvent using a cellulose semipermeable membrane to remove the monomeric compound, and the target product, tri A block polymer was obtained. The compound was identified using NMR and GPC. Mn = 33985 and Mw / Mn = 1.36. The polymerization ratio was A: B: C = 200: 100: 30. The polymerization ratio of the two monomers in the B block was 1: 1.

Further, the block polymer obtained here was hydrolyzed in a mixed solution of dimethylformamide and sodium hydroxide to obtain a triblock polymer in which the C block component was hydrolyzed to form sodium chloride. The compound was identified using NMR and GPC.
Further, the triblock polymer in which the C component became free sulfonic acid was obtained by neutralizing with 0.1N hydrochloric acid in an aqueous dispersion. The compound was identified using NMR and GPC.

Example 4
15 parts by mass of the sulfonate type block polymer obtained in Example 3 and 7 parts by mass of Oil Blue N (CI Solvent Blue-14, manufactured by Aldrich) were co-dissolved in 150 parts by mass of dimethylformamide, It converted into the water phase using 400 mass parts of NaOH aqueous solution, and obtained the ink composition which is pH10. After standing for 10 days, oil blue did not separate and precipitate. In addition, as described above, the inclusion of the coloring material and the hydrophobic polymer was confirmed using EF-TEM observation by cryotransfer, elemental analysis by EELS, and stimulation responsiveness of the ABC block polymer in the coloring material dispersion.

  The ink composition obtained above was filled in a print head of an ink jet printer (BJF800, manufactured by Canon Inc.) and discharged onto a recording medium to obtain an image. As the recording medium, plain paper sprayed with hydrochloric acid was used, and a recording medium capable of giving stimulation was prepared. The recording medium and the dispersion composition were evaluated using the following methods (1) to (2).

  (1) A 50 mm × 50 mm square was printed with the above printer, and when the recording part was strongly pressed with the finger 30 seconds after printing, the ink did not adhere to the finger. This is thought to be because the triblock polymer in the ink composition increased in viscosity after printing, and the fixing speed was increased, and in addition, the triblock polymer contained a coloring material, and thus the scratch resistance was improved. It is done.

  (2) A 50 mm × 50 mm square was printed with the printer, and after 30 seconds of printing, the image was strongly rubbed 5 times with a line marker, and no blue blur was observed. This is thought to be because the triblock polymer in the ink composition increased in viscosity after printing, and the fixing speed was increased, and in addition, the triblock polymer contained a coloring material, and thus the scratch resistance was improved. It is done.

Comparative Example 2
Black self-dispersion pigment (trade name CAB-0-JET300, manufactured by Cabot Corporation) 2 parts by mass, surfactant (Nonion E-230, manufactured by NOF Corporation) 0.5 parts by mass, ethylene glycol 5 parts by mass, and ions 92.5 parts by mass of exchange water was mixed to prepare an ink composition.
As the recording medium, plain paper sprayed with hydrochloric acid prepared in Example 2 and plain paper not sprayed were used. Evaluation was performed in the same manner as in Example 2.

  (1) A square of 50 mm × 50 mm was printed with the above printer with a solid, and the recording part was strongly pressed with a finger 30 seconds after printing. In both cases where the plain paper sprayed with hydrochloric acid and the plain paper not sprayed were used as the recording medium, the ink adhered to the finger.

  (2) A 50 mm × 50 mm square was printed with the printer using a solid, and after 30 seconds of printing, the image was rubbed once with a line marker. In both cases where plain paper sprayed with hydrochloric acid and plain paper not sprayed were used as the recording medium, blue bleeding was observed.

Comparative Example 3
<Synthesis of poly (hydroxystyrene-b-styrene-b-methacrylic acid)>
In a high vacuum system at −78 ° C., 100 ml of 10 mM n-BuLi / THF was added and stirred, then 0.15 mol of t-butoxystyrene was heated and evaporated, and added to the cooled solvent to polymerize the A segment. . After completion of the A segment polymerization, a solvent obtained by diluting 0.15 mol of styrene with 80 ml of THF was added through a breakable seal provided in the system. After completion of the B segment polymerization, a solution prepared by diluting 0.1 mol of t-butyl methacrylate with 60 ml of THF was added by a breakable seal method. Finally, after completion of the C segment polymerization, quenching methanol was added by a breakable seal method to stop the reaction.

  The reaction mixture solution was reprecipitated into a methanol solvent, and the precipitate was collected using a glass filter. The precipitate was vacuum-dried, and confirmed to be the target triblock polymer by analysis using NMR and GPC. Mn = 38200, Mw / Mn = 1.33, polymerization ratio A: B: C = 150: 150: 50.

  Furthermore, the block polymer obtained here was hydrolyzed using hydrobromic acid to obtain a triblock polymer in which the A and C block components were hydrolyzed. The compound was identified using NMR and GPC.

  15 parts by mass of the obtained triblock polymer and 7 parts by mass of Oil Blue N (CI Solvent Blue-14, manufactured by Aldrich) were co-dissolved in 150 parts by mass of dimethylformamide, and 400 parts by mass of NaOH aqueous solution was used. An ink composition having a pH of 11 was obtained by converting to an aqueous phase.

  When printing was performed in the same manner as in Example 4 using the ink composition, faintness (portion where printing was not performed) was confirmed. Precipitates were seen on the printer head. This is probably because the polymer was decomposed in a high-temperature alkaline environment.

Comparative Example 4
A styrene and styrene sulfonate diblock polymer (Mn = 17600, Mw / Mn = 1.33, polymerization ratio 150: 50) was synthesized in the same manner as in Comparative Example 3, and the sulfonate was hydrolyzed by hydrolysis. A decomposed diblock polymer was obtained.

15 parts by mass of the obtained diblock polymer and 7 parts by mass of Oil Blue N (CI Solvent Blue-14, manufactured by Aldrich) were co-dissolved in 150 parts by mass of dimethylformamide, and 400 parts by mass of NaOH aqueous solution was used. An ink composition having a pH of 10 was obtained by converting to an aqueous phase.
As the recording medium, plain paper sprayed with hydrochloric acid prepared in Example 2 and plain paper not sprayed were used. Evaluation was performed in the same manner as in Example 2.

  (1) A square of 50 mm × 50 mm was printed with the above printer with a solid, and the recording part was strongly pressed with a finger 30 seconds after printing. In both cases where the plain paper sprayed with hydrochloric acid and the plain paper not sprayed were used as the recording medium, the ink adhered to the finger.

  (2) A 50 mm × 50 mm square was printed with the printer using a solid, and after 30 seconds of printing, the image was strongly rubbed once with a line marker. When the plain paper sprayed with hydrochloric acid and the plain paper not sprayed were used as the recording medium, blue bleeding was observed.

  Since the block polymer compound of the present invention can satisfactorily disperse the coloring material in a solvent, the functional material is a pigment or dye, the solvent is water, and the dispersibility of the pigment or dye is used. Can be used for a good ink composition.

  The ink composition of the present invention can be used in an ink jet recording method and a recording apparatus having improved fixability to a recording medium and good dispersibility stability of a functional substance such as a pigment or dye in a solvent.

It is a figure which shows the general | schematic mechanism of the ink provision apparatus of this invention.

Explanation of symbols

20 Inkjet recording device 50 CPU
52 X motor drive circuit 54 Y motor drive circuit 56 X direction drive motor 58 Y direction drive motor 60 Head drive circuit 62 X encoder 64 Y encoder 66 Program memory 70 Head

Claims (9)

An ABC triblock polymer having three block segments composed of a polyalkenyl ether main chain, wherein the A segment of the block polymer is hydrophilic or hydrophobic, the B segment is hydrophobic, and the C segment is an ion A block polymer compound having a block segment having a repeating unit structure represented by the following general formula (1) in at least one block segment of the block polymer.

[Wherein, R _a , R _b and R _c are each independently H or CH ₃ . R ¹ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or — (CH (R ² ) —CH (R ³ ) —O) ₁ —R ⁴ or — (CH ₂ ) _m — ( O) selected from _n- R ⁴ . l and m are each independently selected from an integer of 1 to 12, and n is 0 or 1. R ² and R ³ are each independently H or CH ₃ . R ⁴ is H, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, —Ph, —Pyr, —Ph—Ph, —Ph—Pyr, —CHO, —CH ₂ CHO, —CO—CH. ═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ , —CH ₂ COOR ⁵ , —PhCOOR ⁵ , —CH ₂ SO ₃ R ⁵ , —PhSO ₃ R ⁵ , and R ⁴ is other than a hydrogen atom In this case, a hydrogen atom on the carbon atom can be substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, and a carbon atom in the aromatic ring can be substituted with a nitrogen atom. R ⁵ represents H, an alkyl group having 1 to 5 carbon atoms, or a monovalent to polyvalent cation. ]   2. The block polymer compound according to claim 1, wherein the ionic C segment has at least one selected from carboxylic acid, carboxylate, sulfonic acid and sulfonate in its side chain.   A composition comprising the ABC triblock polymer according to claim 1, a functional substance, and a solvent.   The composition of claim 3, wherein the solvent is an aqueous solvent.   An ink composition comprising the ABC triblock polymer according to claim 1, a coloring material, and a solvent.   The ink composition according to claim 5, wherein the solvent is an aqueous solvent.   The ink composition according to claim 5 or 6, wherein the ink composition is an inkjet ink composition.   An ink application method comprising the steps of preparing the ink composition according to claim 5 and applying the ink composition to a medium.   6. An ink comprising: an ink applying means for applying energy to the ink composition according to claim 5 to apply ink to a medium; and a driving means for driving the ink applying means. Granting device.

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