JP2006307066A - Block polymer compound, composition containing the same, ink composition, liquid imparting method using the ink composition and liquid imparting apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a block polymer compound which is capable of properly dispersing a functional material comprising a dye or a pigment in a solvent, and to provide an ink composition excellent in water resistance, where the lining projection of printing image is suppressed. <P>SOLUTION: The block polymer has at least two or more of block segments wherein the at least one of the block segments of the block polymer contains a repetition unit having an organic acid or an organic acid derivative comprising a polycyclic aromatic group as a side chain and a repetition unit having an organic acid or an organic derivative comprising a monocyclic aromatic group or an aliphatic group. The ink composition contains the block polymer compound, a solvent or a dispersing medium and a coloring material. The ink composition is used for an ink jet apparatus. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel block polymer compound useful as various functional materials, a polymer-containing composition containing the compound, an ink composition, a liquid application method and a liquid application apparatus using the ink composition. In particular, the present invention has a functional substance dispersion composition that is an aqueous dispersion material, and is preferably useful as an ink composition of an image forming material that can be used in a printer, a display, or the like, and a liquid application method using the ink composition And a liquid applicator.

  Aqueous dispersion materials containing granular solids conventionally have functional materials such as herbicides, pesticides such as insecticides, drugs such as anticancer agents, antiallergic agents and anti-inflammatory agents, or colorants as granular solids. Color materials such as ink and toner are well 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 technique is a method in which ink supplied from an ink tank is heated by a heater in a nozzle to evaporate and foam, and 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.

  Since the ink used in these ink jet methods uses an aqueous solution of a normal dye that is soluble in water, a phenomenon of seeping out to the back side (hereinafter referred to as a show-through) may appear, or improvement in water resistance may occur. It was sought after. For example, when there is little show-through, it is possible to print images on both sides of plain paper, which is useful for reducing the number of paper and saving resources. In order to improve these, a method of adding an alginate or the like to a resin-dispersed pigment or color material particle-containing ink has been proposed.

However, these methods use a lot of non-aqueous solvents and have high affinity for the head constituent materials, etc., causing swelling and dissolution, and stable dispersion of ink for a long time. In this respect, further improvements are desired. In addition, after printing, ink show-through is seen, and further improvement in water resistance is desired (for example, see Patent Document 1).
JP-A-7-109430 (pages 2 and 3)

The present invention has been made in view of such problems of the prior art, and provides a block polymer compound capable of satisfactorily dispersing a functional substance in a solvent.
The present invention also provides an ink composition in which the functional substance is a pigment or dye, the solvent is water, the dispersibility of the pigment or dye is good, and the fixing property to a recording medium is excellent. It is.

The present invention also provides an ink composition for inkjet which has high dispersibility stability of a functional substance such as pigment or dye in a solvent, no show-through, and good water resistance.
The present invention also provides a liquid application method using the above ink composition and a liquid application apparatus used therefor.

The above problems are solved by the present invention described below.
A first aspect of the present invention is a block polymer compound having at least two or more block segments, wherein at least one block segment of the block polymer compound has hydrophobicity and hydrophilicity. It is a block polymer compound characterized in that it contains at least one repeating unit structure which is nonionic.

The block polymer compound is preferably amphiphilic.
The block polymer compound preferably contains a hydrophobic block segment and a hydrophilic block segment.

The block polymer compound preferably has three or more block segments.
The block polymer preferably contains a polyalkenyl ether structure as a repeating unit structure, and more preferably contains a polyvinyl ether structure as a repeating unit structure.

  The hydrophobic repeating unit structure represented by the following general formula (1), and the hydrophilic repeating unit structure that is nonionic is a repeating unit represented by the following general formula (2). Is preferred.

Wherein R ¹ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, Ph, Pyr, Ph-Ph, Ph-Pyr, — (CH (R ² ) —CH (R ³ ) -O) _p -R ⁴ and _{- (CH 2) m - (} O) is selected from _n -R ^4, hydrogen atoms in the aromatic ring is a linear or branched alkyl group having 1 to 4 carbon atoms And a carbon atom in the aromatic ring may be substituted with a nitrogen atom, p is an integer of 1 to 18, m is an integer of 1 to 36, and n is 0 or 1. R ² , R ³ is each independently a hydrogen atom or CH _3. R ⁴ is a linear, branched or cyclic alkyl group having 4 to 18 carbon atoms, Ph, Pyr, Ph-Ph, Ph-Pyr, -CHO, -CO-CH = CH ₂ or _{-CO-C (CH 3) =} CH 2, a -CH ₂ COOR ^5, carbon atoms The bonded hydrogen atom may be a linear or branched alkyl group having 1 to 4 carbon atoms or F, Cl or Br, and the carbon atom in the aromatic ring may be substituted with a nitrogen atom. R ⁴ is a linear, branched or cyclic alkyl group having 3 carbon atoms, p is an integer of 1 to 3, and a hydrogen atom bonded to a carbon atom is a straight chain having 1 to 4 carbon atoms. A chain or branched alkyl group or F, Cl, Br, and a carbon atom in the aromatic ring may be substituted with a nitrogen atom, and R ⁵ is an alkyl group having 1 to 4 carbon atoms. In addition, -Ph represents a phenyl group, -Pyr represents a pyridyl group, -Ph-Ph represents a biphenyl group, and -Ph-Pyr represents a pyridylphenyl group.Pyridyl group, biphenyl group, and pyridylphenyl group have possible positional isomerism. Any of the body It may be.)

Wherein R ⁶ is selected from a hydrogen atom or — (CH (R ⁷ ) —CH (R ⁸ ) —O) _p —R ⁹ and — (CH ₂ ) _m — (O) _n —R ^9. Is an integer from 1 to 18, m is an integer from 1 to 36, and n is 0 or 1. R ⁷ and R ⁸ are each independently a hydrogen atom or —CH ₃ , R ⁹ is a hydrogen atom and has 1 carbon atom. Represents a linear, branched or cyclic alkyl group from 1 to 2, R ⁹ is a linear, branched or cyclic alkyl group having 3 carbon atoms, and p is an integer of 4 to 18. )

  At least one type of repeating unit structure showing nonionicity in the block segment containing at least one type of repeating unit structure showing hydrophobicity and at least one type of repeating unit structure showing hydrophilicity and nonionicity The content of is preferably 50 mol% or more.

The second of the present invention is a polymer-containing composition comprising the first block polymer compound of the present invention, a solvent or dispersion medium, and a functional substance.
It is preferable that the functional substance is included in the block polymer.

It is preferable that the functional substance is a color material.
Further, the polymer-containing composition can be used as an ink composition.
The ink composition is preferably an ink-jet ink composition.

According to a third aspect of the present invention, there is provided a liquid application method using the above ink composition.
In a liquid application method in which ink is ejected from an ink ejection part and applied onto a recording medium for recording, the ink is preferably the ink composition described above.

It is preferable that the ink is discharged from the ink discharge portion by applying thermal energy to the ink.
According to a fourth aspect of the present invention, there is provided a liquid applicator characterized by being used in the liquid applicator method described above.

ADVANTAGE OF THE INVENTION According to this invention, the block polymer compound which can disperse | distribute a functional substance favorably to a solvent can be provided.
In addition, the present invention can provide an ink composition using the block polymer compound, in which the functional substance is a pigment or dye, the solvent is water, and the pigment or dye has good dispersibility. In addition, the present invention can provide an ink composition in which show-through and suppression are suppressed when printing on a recording medium and water resistance is improved.

In addition, the present invention can provide an ink composition for inkjet which has good dispersibility stability of a functional substance such as pigment or dye in a solvent.
In addition, the present invention can provide a liquid application method using the above ink composition and a liquid application apparatus used therefor.

Hereinafter, the present invention will be described in detail.
A first aspect of the present invention is a block polymer compound having at least two or more block segments, wherein at least one block segment of the block polymer compound has hydrophobicity and hydrophilicity. It is a block polymer compound characterized in that it contains at least one repeating unit structure which is nonionic.

Preferably, the block polymer compound is an amphiphilic block polymer compound.
In the block polymer compound of the present invention, at least one block segment is lyophobic and at least one block segment is amphiphilic, so that amphiphilicity is manifested. As the lyophobic and amphiphilic target, an aqueous solvent is preferable. In other words, the block polymer compound of the present invention preferably has at least one hydrophobic segment and one hydrophilic segment. More preferably, it has 3 or more types of block segments. The block polymer compound is more preferably in a block form such as ABA, ABC, ABCD type, ABCA type.

  The block polymer is a copolymer in which different types of polymer segments are linked to a polymer chain, and is also called a block copolymer or a block polymer. Moreover, a block segment shows the partial structural component of the block polymer which consists of at least 1 type of repeating unit structure.

  Specific examples of block polymer compounds that can be used in the present invention include acrylic, methacrylic block polymers, polystyrene and other addition polymerization or condensation polymerization block polymers, polyoxyethylene, and polyoxyalkylene. A block polymer compound having a block can also be used.

  In the present invention, a block polymer compound containing a polyalkenyl ether structure is preferably used, and a block polymer compound containing a polyvinyl ether structure is more preferably used. In the present invention, the block polymer compound may be a graft polymer compound containing a polyvinyl ether structure, or a segment having the block polymer compound may be a copolymer segment or a gradient segment.

  The block polymer compound containing a polyvinyl ether structure preferably used in the present invention will be described. A number of methods for synthesizing a polymer containing a polyvinyl ether structure have been reported (for example, JP-A-11-080221), but methods using cationic living polymerization by Aoshima et al. (JP-A-11-322942 and JP-A-11-322866). Publication) is a typical example. By conducting polymer synthesis using cationic living polymerization, various polymers such as homopolymers and copolymers composed of two or more monomers, as well as block polymer compounds and graft polymer compounds are precisely aligned in length (molecular weight). Can be synthesized.

For example, by gradually adding another vinyl ether monomer during the polymerization of one vinyl ether monomer, a polymer (gradient copolymer) in which the monomer composition gradually changes along the polymer chain is synthesized and blocked. Compared to the case of polymer compounds, the effect of differences in monomer sequence distribution on thermal stimulus responsiveness has been reported (Polymer Preparints, Japan Vol. 51, No. 7 (2002)). In addition, various functional groups can be introduced into the side chain of polyvinyl ether. The cationic polymerization method can also be carried out in the HI / I ₂ system, HCl / SnCl ₄ system, or the like.

The structure of the block polymer compound containing a polyvinyl ether structure may be a copolymer composed of vinyl ether and another polymer.
It is preferable that at least one type of repeating unit structure exhibiting hydrophobicity used in the present invention contains a repeating unit represented by the following general formula (1).

In the formula, R ¹ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, Ph, Pyr, Ph-Ph, Ph-Pyr, — (CH (R ² ) —CH (R ³ ). -O) _p -R ⁴ and _{- (CH 2) m - (} O) is selected from _n -R ^4, hydrogen atoms in the aromatic ring is a linear or branched alkyl group having 1 to 4 carbon atoms The carbon atom in the aromatic ring may be substituted with a nitrogen atom.

p is an integer of 1 to 18, m is an integer of 1 to 36, and n is 0 or 1.
R ² and R ³ are each independently a hydrogen atom or CH ₃ .
R ⁴ is a linear, branched or cyclic alkyl group having 4 to 18 carbon atoms, Ph, Pyr, Ph-Ph, Ph-Pyr, —CHO, —CO—CH═CH ₂ or —CO—C ( CH ₃ ) ═CH ₂ , —CH ₂ COOR ⁵ , and the hydrogen atom bonded to the carbon atom is a linear or branched alkyl group having 1 to 4 carbon atoms or F, Cl, Br, and aromatic Each carbon atom in the group ring may be substituted with a nitrogen atom.

R ⁴ is a linear, branched or cyclic alkyl group having 3 carbon atoms, p is an integer of 1 to 3, and a hydrogen atom bonded to a carbon atom is a straight chain having 1 to 4 carbon atoms. A chain or branched alkyl group or F, Cl, Br, and a carbon atom in the aromatic ring may each be substituted with a nitrogen atom.

R ⁵ is an alkyl group having 1 to 4 carbon atoms.
In the present invention, -Ph represents a phenyl group, -Pyr represents a pyridyl group, -Ph-Ph represents a biphenyl group, and -Ph-Pyr represents a pyridylphenyl group. The pyridyl group, biphenyl group and pyridylphenyl group may be any of the possible positional isomers.

  Specific examples of the repeating unit structure represented by the general formula (1) are shown below, but are not limited thereto.

(R represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.)
Moreover, it is preferable that the hydrophobic block segment of the amphiphilic block polymer used in the present invention contains the repeating unit represented by the general formula (1).

  When the nonionic repeating unit structure used in the present invention exhibits hydrophilicity, when the functional substance is encapsulated and dispersed in the block polymer compound, it can be dispersed more stably.

  It is preferable that the hydrophilic and nonionic repeating unit structure used in the present invention contains a repeating unit represented by the following general formula (2).

In the formula, R ⁶ is selected from a hydrogen atom or — (CH (R ⁷ ) —CH (R ⁸ ) —O) _p —R ⁹ and — (CH ₂ ) _m — (O) _n —R ⁹ .
p is an integer of 1 to 18, m is an integer of 1 to 36, and n is 0 or 1.

R ⁷ and R ⁸ are each independently a hydrogen atom or —CH ₃ .
R ⁹ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 2 carbon atoms. R ⁹ is a linear, branched or cyclic alkyl group having 3 carbon atoms, and p is an integer of 4 to 18.

  Although the specific example of the repeating unit structure which shows the hydrophilic property represented by General formula (2) is given below, it is not limited at all.

  In the present invention, at least one hydrophobic repeating unit represented by the general formula (1) and at least one hydrophilic non-ionic repeating unit structure represented by the general formula (2) It is preferable that the content of at least one repeating unit structure exhibiting nonionicity and hydrophilicity is 50 mol% or more in the segment containing. When the content of at least one type of repeating unit structure showing nonionicity and hydrophilicity is 50 mol% or more, the functional substance is more stably dispersed when encapsulated and dispersed in the block polymer compound. It is possible and preferred. Further, when recording on a recording medium by a thermal ink jet method in which a polymer-containing composition containing the block polymer compound is applied as an ink composition and foamed by applying thermal energy to perform recording, more stable ejection is achieved. It is preferable to be obtained.

  Further, it contains at least one hydrophobic repeating unit represented by the general formula (1) and at least one hydrophilic non-ionic repeating unit structure represented by the general formula (2). It is preferable that the segment to show hydrophilicity. By exhibiting hydrophilicity, when the functional substance is encapsulated and dispersed in the block polymer compound, it is more preferable because it can be dispersed more stably.

  The block polymer compound of the present invention preferably has three or more types of block segments. The hydrophobic block segment having at least one type of repeating unit structure represented by the general formula (1) and the general Hydrophilicity having at least one repeating unit structure exhibiting hydrophobicity represented by the formula (1) and at least one repeating unit structure represented by the general formula (2) that is hydrophilic and nonionic It is preferable to have an ionic block segment and a block segment exhibiting anionic property. A block polymer compound having a hydrophobic block segment, a hydrophilic block segment, and an anionic block segment forms micelle particles composed of a hydrophobic segment in the core portion and a hydrophilic segment in the shell portion in an aqueous solvent. Micellar particles can encapsulate a functional substance in the core. Further, since the shell portion has an anionic segment, it can be stably dispersed by electrical repulsion between micelle particles. Therefore, for example, when the functional substance is a color material, it is possible to form a color material-containing ink composition.

  In addition, the hydrophobicity in the present invention means the property of a substance or molecule (part thereof) that has a low affinity for water, that is, hardly dissolves in water or hardly mixes with water. The hydrophilicity in the present invention indicates a property of being easily soluble or mixed in water by having polarity or electric charge.

  The repeating unit structure exhibiting anionic property is not particularly limited, but is a repeating unit structure having a carboxylic acid in the side chain, such as a polymer obtained by polymerizing acrylic acid, methacrylic acid or the like.

  In the repeating unit structure having an anionic property on the above side chain, for example, having a carboxylic acid, the meaning of the side chain is not directly connected to the main chain of the polymer, but the carboxylic acid is present through some linking group It means to do. For example, it refers to a form in which a carboxylic acid is present via a linking group such as an alkylene group or an alkyleneoxy group, rather than being directly connected to the main chain as in a polymer polymer of acrylic acid or methacrylic acid. .

  The linking group preferably has 3 or more atoms from the main chain. More preferably, there are 5 or more atoms, and it is preferable that the carboxylic acid is sufficiently separated from the main chain. This is because in a structure that is directly connected to the main chain too much, the carboxylic acid's mobility is limited, so that the interaction between molecules and within the molecule may not be sufficiently exerted. Accordingly, a free carboxylic acid structure can be mentioned as a preferred form as one that can further interact with them.

  It is preferable that the repeating unit structure showing anionic property of the amphiphilic block polymer compound used in the present invention is the following general formula (3).

Wherein, R ¹⁰ is -X-COO ^- represents a. X is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or — (CH (R ¹¹ ) —CH (R ¹² ) —O) _p — (CH ₂ ) _m — or — (CH ₂ ) _m— (O) _n — (CH ₂ ) _q — or a structure in which at least one of the methylene groups is substituted with a carbonyl group or an aromatic ring structure.

p represents an integer of 1 to 18. m represents an integer of 1 to 36.
n represents 1 or 0. q represents an integer of 1 to 18.
R ¹¹ and R ¹² represent an alkyl group. R ¹¹ and R ¹² may be the same or different.

  Although the specific example of the repeating unit structure which shows anionic property represented by General formula (3) is given below, it is not limited at all.

(Ph represents a phenylene group.)
The number average molecular weight (Mn) of the block polymer compound of the present invention is 200 or more and 10000000 or less, and the range preferably used is 1000 or more and 1000000 or less. If it exceeds 10000000, the entanglement between the polymer chains and between the polymer chains becomes excessive, and it is difficult to disperse in the solvent. If it is less than 200, the steric effect as a polymer may be difficult to obtain due to the low molecular weight. The preferable degree of polymerization of each block segment is 3 or more and 10,000 or less. More preferably, it is 5 or more and 5000 or less. More preferably, it is 10 or more and 4000 or less.

  The molecular weight distribution Mw (weight average molecular weight) / Mn (number average molecular weight) of the block polymer compound used in the present invention is preferably 2.0 or less. More preferably, it is 1.6 or less.

  Further, in order to improve dispersion stability and inclusion, it is preferable that the molecular mobility of the block polymer is more flexible because it has a point of being easily entangled and compatible with the surface of the functional substance. For this purpose, the glass transition temperature Tg of the main chain of the block polymer is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and further preferably −20 ° C. or lower. Also in this respect, a polymer having a polyvinyl ether structure is preferably used because it generally has a soft property having a low glass transition point.

Next, the second invention of the present invention will be described.
A second invention of the present invention is a polymer-containing composition comprising a solvent or dispersion medium, a functional substance, and the first block polymer compound of the present invention. The above-mentioned polymer compound and a functional substance having a useful predetermined function such as a coloring material are contained, and the polymer compound can be suitably used for favorably dispersing the functional substance or the like.

  The functional substance is a substance having a predetermined function, and includes, for example, compounds, mixtures, solids, liquids, and other forms of substances. For example, substances that can be used in agricultural chemicals such as herbicides and insecticides, Substances that can be used as pharmaceuticals such as cancer agents, antiallergic agents, anti-inflammatory agents, substances that can be used in cosmetics such as lipsticks, foundations, blushers, moisturizing creams, coloring materials such as dyes, pigments, coloring pigments, and compositions thereof Can give. In the present invention, coloring materials such as dyes, pigments and colored pigments are preferably used.

  In the present invention, the functional substance and the block polymer compound are dispersed in the solvent as particles, but as the particles dispersed in the solvent, a functional substance having a predetermined function is dispersed alone. Particles in which the functional substance is adsorbed and dispersed in the hydrophilic portion of the block polymer compound, particles in which the functional substance is encapsulated in the block polymer compound, and particles formed by the block polymer compound alone. Can be mentioned. It is preferable that all functional substances having a predetermined function are included in the block polymer compound. The state in which the functional substance is encapsulated in the block polymer compound is preferably a state in which the functional substance is encapsulated in the polymer micelle formed by the block polymer compound.

  The content of the functional substance having a predetermined function contained in the polymer-containing composition of the present invention is 0.1% by mass or more and 70% by mass or less. Preferably they are 0.5 mass% or more and 50 mass% or less. More preferably, it is 1 mass% or more and 30 mass% or less. When the amount is less than 0.1% by mass, the predetermined function may not be exhibited. When the amount exceeds 70% by mass, the viscosity of the composition may be too high.

The polymer-containing composition of the present invention can be stably dispersed in an aqueous solvent.
This is because the amphiphilic block polymer compound used in the present invention encapsulates a coloring material in the core portion, the shell portion forms micelles composed of hydrophilic block segments, and the coloring material is dispersed in an aqueous solvent. be able to. That is, it is possible to form a color material-encapsulated ink composition.

  Furthermore, since the shell part of the micelle has an anionic repeating unit structure at the same time, the polymer micelle particles enclosing the coloring material also show an anionic property. Therefore, the aggregation between the polymer micelle particles is suppressed by electric repulsion and can be stably dispersed in the solvent, and the particles of the dispersion composition can have a uniform particle size. Furthermore, it is preferable to encapsulate the coloring material with a polymer from the viewpoint that the environmental stability can be improved. The functional substance is encapsulated in the polymer micelle because, for example, the functional substance does not disperse in the solvent in the absence of the polymer micelle. It can be confirmed by separating them. It can also be confirmed by an electron microscope or the like.

  Interaction between particles, particle size of dispersed particles, and uniformity of particle size greatly affect the dispersion stability of a colorant-dispersed ink in which the polymer-containing composition of the present invention is applied to an ink composition. That is, if aggregation occurs between the particles dispersed in the solvent, the particles grow greatly and precipitate as a result, and a stable ink dispersion composition cannot be obtained.

  Further, the polymer-containing composition of the present invention is used as an ink composition and has no show-through and water resistance when recorded on a recording medium by a thermal ink jet method in which thermal energy is applied to perform foaming and recording. An image with excellent properties can be obtained.

  When the ink composition lands on the recording medium, the aqueous solvent penetrates into the paper. On the other hand, since the micelle formed by the block polymer compound of the present invention in an aqueous solvent has a repeating unit structure exhibiting hydrophobicity in the shell portion, the affinity to the aqueous solvent is suppressed, and therefore, together with the aqueous solvent. Permeation into the paper is suppressed and no show-through occurs. Further, when an aqueous solvent is added from the outside after image formation, image bleeding is suppressed. Since this has a repeating unit structure which shows hydrophobicity in the block segment which shows hydrophilicity, the solubility with respect to an aqueous solvent is suppressed and bleeding does not arise.

  In addition, basic additives such as calcium hydroxide and sodium hydroxide are added in order to anionize a functional group showing anionicity such as a carboxyl group. As a result, the polymer micelle particles are also sufficiently anionized, Aggregation is suppressed by electrical repulsion, and stable dispersion can be achieved in a solvent. In addition, when recording the ink composition of the present invention on a recording medium by a thermal ink jet method in which thermal energy is applied to perform recording, the ink composition is stable without precipitation and aggregation and without clogging of the nozzle. Can be discharged. Furthermore, there is no ink ejection failure when ejection is stopped for a while, and stable image formation can be performed.

The average particle size of the block polymer micelle particles can be measured by a photon correlation method or the like. The present invention mainly uses measurement by a dynamic light scattering method which is a photon correlation method. In general, the dispersion index μ / G ² (μ: second-order coefficient of cumulant expansion, G: attenuation constant) shown by Gulari et al. Is used as an index of particle size uniformity (The Journal of Chemical Physics). 70, 3965, 1979). This value is also determined by the dynamic light scattering method. As a particle size measuring device by the dynamic light scattering method, there is a device such as DLS7000 manufactured by Otsuka Electronics Co., Ltd.

  Furthermore, the block polymer having a polyvinyl ether structure in the present invention has a glass transition temperature of the main chain of 20 ° C. or less and a flexible molecular mobility. Therefore, when the ink composition of the present invention is ejected and image-formed on a recording medium, the ink composition of the present invention is well entangled with the coloring material and the recording medium, and the coloring material is sufficiently encapsulated in the polymer micelle to form an image and recording It exhibits high fixability to the medium.

A composition in which a coloring material such as a dye, pigment, or colored pigment is used as the functional substance contained in the composition of the present invention is preferably used as an ink composition.
The ink composition of the present invention will be described.

Specific examples of dyes, organic pigments and inorganic pigments used in the ink composition are shown below.
In addition, the dye that can be used in the present invention may be a known dye, such as a direct dye, an acid dye, a basic dye, a reactive dye, a water-soluble dye for food coloring, or an insoluble pigment for a disperse dye as described below. Can be used.

For example, as the oil-soluble dye, C.I. I. Solvent Blue, −33, −38, −42, −45, −53, −65, −67, −70, −104, −114, −115, −135;
C. I. Solvent Red, −25, −31, −86, −92, −97, −118, −132, −160, −186, −187, −219;
C. I. Solvent Yellow, -1, -49, -62, -74, -79, -82, -83, -89, -90, -120, -121, -151, -153, -154 and the like.

Examples of 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.

These examples of the color material are particularly preferable for the ink composition of the present invention, but the color material used in the ink composition of the present invention is not particularly limited to the color material. .
In the present invention, pigments and dyes may be used in combination.

  The dye used in the ink composition 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 may not be obtained, and when it exceeds 50% by mass, the viscosity may be excessively increased. A more preferable range is from 0.5% by mass to 30% by mass.

  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 three primary color pigments of cyan, magenta, and yellow. Color pigments other than those described above, colorless or light color pigments, metallic luster pigments, and the like may be used. In the present invention, a commercially available pigment may be used, or a newly synthesized pigment may be used.

The following are examples of commercially available pigments for black, cyan, magenta, and yellow.
Black pigments include Raven1060, Raven1080, Raven1170, Raven1200, Raven1250, Raven1255, Raven1500, Raven2000, Raven3500, Raven5250, Raven5750, Raven7000, Raven5000U, Raven5000U, Raven5000U L, MOGUL-L, Regal 400R, Regal 660R, Regal 330R, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1300, Monarch 1400 (above, manufactured by Cabot Corporation), Color Black FW1, olor Black FW2, Color Black FW200, Color Black 18, Color Black S160, Color Black S170, Special Black 4, Special Black 4A, Special Black 6, Printex35, PrintexU, Printex140U, 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 composition 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 may not be obtained, and when it exceeds 50% by mass, the viscosity may be excessively increased. A more preferable range is from 0.5% by mass to 30% by mass.

  The solvent contained in the ink composition of the present invention is not particularly limited, but means a medium capable of dissolving, suspending, and dispersing the components contained in the ink composition. In the present invention, organic solvents such as various linear, branched and cyclic aliphatic hydrocarbons, aromatic hydrocarbons and heteroaromatic hydrocarbons, aqueous solvents, water and the like are included as the solvent.

In particular, water and an aqueous solvent can be preferably used in the ink composition of the present invention.
Examples of the aqueous solvent include, for example, polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether. And polyhydric alcohol ethers such as diethylene glycol monoethyl ether and diethylene glycol monobutyl ether, and nitrogen-containing solvents such as N-methyl-2-pyrrolidone, substituted pyrrolidone and triethanolamine. In addition, as a use of ink, monohydric alcohols such as methanol, ethanol, isopropyl alcohol and the like can be used for the purpose of speeding up drying on paper.

  The content of the water and the aqueous solvent in the ink composition of the present invention is preferably used in the range of 20 to 95% by mass with respect to the total weight of the aqueous dispersion. More preferably, it is the range of 30-90 mass%. In addition, the polymer-containing composition of the present invention can contain additives such as ultraviolet absorbers, antioxidants, stabilizers, etc. without preventing the inclusion of components other than those described above.

  The content of the block polymer compound 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 compound is less than 0.1% by mass, the dye or pigment contained in the ink composition of the present invention may not be sufficiently dispersed. When the amount exceeds 50% by mass, the viscosity increases. It may be too much.

  In addition, a preferred embodiment of the present invention is a functional substance dispersion composition having a pH value of 5 or more and having a substance and a block polymer dispersed as particles in a solvent. More preferably, the pH value is 7 or more.

  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 stimulus species to be given, an appropriate species is selected for forming an image from temperature change, exposure to electromagnetic waves, change in pH, change in concentration, 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, “stimulation” includes changes in temperature; application of an electric field; exposure to light (electromagnetic waves) such as ultraviolet light, visible light, or infrared; change in pH of the composition; addition of chemicals; Can be mentioned.

  Preferred stimuli in the present invention 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).

  Various properties (states and characteristics) that change in the composition of the present invention can be selected depending on the intended use of the composition of the present invention. For example, the composition causes a phase change (for example, a change from a sol to a gel) by stimulation, thereby improving fixability to a recording medium.

  Various additives and auxiliaries can be added to the ink composition of the present invention as necessary. It is also possible to use a resin having both hydrophilic and hydrophobic parts. 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 monoesters of the carboxylic acids, vinyl sulfonic acid, styrene sulfonic acid, vinyl alcohol, acrylamide, methacryloxyethyl phosphate, and the like. Hydrophobic monomers include styrene derivatives such as styrene and α-methylstyrene, vinylcyclohexane, vinylnaphthalene derivatives, acrylic acid esters, and methacrylic acid esters. Of course, both hydrophilic and hydrophobic monomers are not limited to those shown above.

Examples of the additive that may be contained in the composition of the present invention include a crosslinking agent activated by application of heat or electromagnetic waves, an acid generator, a polymerization initiator, and the like.
Other additives that can be added to the composition in the present invention include a pH adjusting agent for stabilizing the ink and the stability of the ink piping in the recording apparatus; and penetrating the ink into the recording medium. Penetration agent that speeds up apparent drying earlier; Antifungal agent that prevents generation of wrinkles in the ink; sequestering metal ions in the ink, depositing metal at the nozzle, and insoluble matter in the ink It includes a chelating agent for preventing precipitation and the like, a defoaming agent for preventing circulation and movement of the recording liquid, and generation of bubbles during production of the recording liquid, an antioxidant, a viscosity adjusting agent, a conductive agent, an ultraviolet absorber and the like.

  The specific content of the ink composition for inkjet which is a preferred embodiment of the ink composition of the present invention will be described below. As a method for producing the inkjet ink composition of the present invention, a block polymer and a coloring material are added to water and a water-soluble solvent, and dispersed using a disperser, and then coarse particles are removed by centrifugation or the like. Subsequently, it can create by adding water or a solvent, an additive, etc., stirring, mixing, and filtering.

  Examples of the disperser include an ultrasonic homogenizer, a laboratory homogenizer, a colloid mill, a jet mill, and a ball mill, and these may be used alone or in combination.

Next, the liquid application method of the present invention will be described.
[Liquid application method]
The ink composition of the present invention can be used in various image devices such as various printing methods, ink jet methods, and electrophotographic methods, and pattern forming devices such as semiconductor processes, and can be drawn by a liquid application method using this device. . The ink composition of the present invention is particularly preferably used in an ink jet method. The ink jet method used may be a known method such as a piezo ink jet method using a piezoelectric element or a thermal ink jet method in which heat energy is applied to perform foaming and recording. In addition, either a continuous type or an on-demand type method may be used. The ink composition of the present invention can also be used in a recording method in which ink is printed on an intermediate transfer member and then transferred to a final recording medium such as paper.

  When the ink composition having stimulus responsiveness according to the present invention is used as an inkjet ink, it can be used, for example, in the following manner in the present invention. The ink can be aggregated by the following stimuli (a) to (d).

(A) When used as an ink that responds to a temperature stimulus The ink composition for inkjet according to the present invention is caused by a temperature stimulus due to a difference between the temperature of the ink in the ink tank and the temperature of the ink on the recording medium attached by ejection. A phase change is caused, and a thickening or insoluble component is agglomerated rapidly.

(B) When used as ink that responds to electromagnetic wave stimulation Electromagnetic wave stimulation is given by a method in which an ink tank is a dark room and exposed to visible light by ejection, or an electromagnetic wave irradiation unit provided in an ink jet recording apparatus. Can do. By the electromagnetic wave stimulation, the polymerizable functional group contained in the inkjet ink composition of the present invention is polymerized to cause thickening or aggregation of insoluble components.

(C) When used as an ink that responds to a stimulus due to a change in pH When the ink adheres to the recording medium, the pH of the ink changes due to the influence of the recording medium. The material undergoes a phase change, and thickening or aggregation of insoluble components occurs.

(D) When an inkjet ink composition that responds to a stimulus due to a change in density is used After the concentration of ink in the ink tank and the water and aqueous solvent contained in the ejected ink are evaporated or absorbed by the recording medium Due to the change in the density of the ink due to the difference from the density, the ink-jet ink composition of the present invention undergoes a phase change, causing thickening or aggregation of insoluble components.

  By modifying the properties of these inks, it is possible to improve color bleeding and feathering, and to exhibit excellent fixing properties. The modification of the ink is not limited to the above-described thickening or aggregation of insoluble components.

  Various methods can be applied to the method of applying the stimulus. As a preferable method, there is a method in which a stimulus-imparting substance serving as a stimulus is mixed or contacted with the aforementioned stimulus-responsive ink. For example, an inkjet method can be applied as a method of mixing a composition having a corresponding pH with the pH-responsive ink of (c). As described in Japanese Patent Laid-Open No. 64-63185, it is possible to drive a stimulus imparting substance that serves as a stimulus over the entire area of an image formation by an ink jet head, or Japanese Patent Laid-Open No. 8-216392. A superior image can also be formed by controlling the amount of stimulus-imparting substance as a stimulus as in the method described.

  It is also possible to use a stimulating substance serving as a stimulus with an ink containing a dye or a pigment. For example, ink that gives a stimulus to one of the cyan-magenta-yellow-black (CMYK) inks used in the color ink jet method is used, and ink that responds to the stimulus is used for any one of the CMYK inks. It is possible to improve. There are various combinations of CMYK for which stimulus-responsive ink is used, and for which other stimulus ink is used. In the present invention, any combination may be used. It is not intended to limit. Further, the kind of stimulating composition and stimulus response ink can be performed in all of the aforementioned stimulus response patterns, and is not particularly limited.

Next, the liquid application apparatus of the present invention will be described.
[Liquid applicator]
The ink jet recording apparatus using the ink composition for ink jet according to the present invention includes an ink jet recording apparatus such as a piezo ink jet system using a piezoelectric element, a thermal ink jet system in which heat energy is applied to perform foaming and recording.

  FIG. 1 is a schematic functional diagram of the ink jet recording apparatus. Reference numeral 50 denotes a central processing unit (CPU) of the ink jet recording apparatus. A program for controlling the CPU 50 may be stored in the program memory 66, or may be stored in storage means such as an EEPROM (not shown) as so-called firmware. The ink jet recording apparatus receives recording data in the program memory 66 from recording data creating means (not shown, computer or the like). The recorded data may be image or character information itself to be recorded, may be compressed information of the information, or may be encoded information. When processing the compressed or encoded information, the CPU 50 can decompress or expand the image or character information to be recorded. An X encoder 62 (for example, related to the X direction or the main scanning direction) and a Y encoder 64 (for example, related to the Y direction or the sub scanning direction) can be provided to notify the CPU 50 of the relative position of the head with respect to the recording medium.

  The CPU 50 transmits a signal for recording an image to the X motor drive circuit 52, the Y motor drive circuit 54, and the head drive circuit 60 based on information of the program memory 66, the X encoder 62, and the Y encoder 64. The X motor drive circuit 52 drives the X direction drive motor 56, and the Y motor drive circuit 54 drives the Y direction drive motor 58, respectively, to move the head 70 relative to the recording medium and move it to the recording position. The head driving circuit 60 transmits signals to the head 70 for discharging various ink compositions (Y, M, C, K) or stimulating substances that become stimuli when the head 70 moves to the recording position. And record. The head 70 may be for ejecting a single color ink composition, may be for ejecting a plurality of types of ink compositions, or ejects a stimulating substance that serves as a stimulus. You may have the function to do.

  In addition, the ink composition of the present invention can be used in an apparatus using a direct recording method in which ink is directly attached to a recording medium. After forming an image with an ink on an intermediate transfer member on which a latent image is formed, paper or the like is used. It can also be used in an indirect recording apparatus using a recording method for transferring to the final recording medium. Also, the present invention can be applied to an apparatus using an intermediate transfer member by a direct recording method.

Next, the recording medium of the present invention will be described.
[Recording medium]
As described above, the stimulus-imparting substance that serves as a stimulus can be mixed with or brought into contact with the stimulus-responsive ink, but a mechanism for giving a stimulus to the recording medium can be provided in advance. For example, a method of recording on acidic paper using acid responsive ink as pH responsive ink; using pH responsive ink as stimulus responsive ink, and changing pH in response to application of heat, electromagnetic waves or pressure A method of recording on a recording medium that releases a substance; using a stimulus-responsive ink containing a functional group capable of crosslinking or polymerization, and releasing a crosslinking agent or a polymerization initiator in response to application of heat, electromagnetic waves or pressure Examples thereof include a method for recording on a recording medium. In the present invention, the recording medium may be in any known form. For example, plain paper, thermal paper, acid paper, etc. can be mentioned.

  When the direct recording method is used, the above recording medium is used as the final recording medium. On the other hand, when the indirect recording method is used, the above-mentioned recording medium may be used as an intermediate transfer member, or may be used as a final recording medium.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
Example 1
<Isobutyl vinyl ether, biphenyloxyethyl vinyl ether (IBVE-r-VEEtPhPh: A block), biphenyloxyethyl vinyl ether, 2-methoxyethyl vinyl ether (VEEEtPhPh-r-MOVE: B block), 4- (2-vinyloxy) ethoxy Synthesis of Triblock Polymer Poly [(IBVE-r-VEEEtPhPh) -b- (VEEEtPhPr-MOVE) -b-VEEtPhCOOEt] Composed of Ethyl Benzoate (VEEEtPhCOOEt: C Block), where b is a block Polymer, r is a symbol indicating a random polymer).

  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, IBVE 2.5 mmol (mmol), VEEtPhPh 2.5 mmol, ethyl acetate 16 mmol, 1-isobutoxyethyl acetate 0.05 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 ethylaluminum 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, 1.5 mmol (mmol) of VEEtPhPh as a B block component and a 1.0 mmol toluene solution of MOVE were added, and polymerization was continued. After confirming the completion of the polymerization of the B block by monitoring using GPC, 5.0 mmol of ethyl 4- (2-vinyloxy) ethoxybenzoate was added as a C block component, and the polymerization was continued. After 3 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 0.6 mol / L 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 = 19800 and Mw / Mn = 1.34. The polymerization ratio was A: B: C = 100: 50: 10. The polymerization ratio of the two types of monomers in the A block was 50:50. The polymerization ratio of the two types of monomers in the B block was 30:20. That is, the content of at least one repeating unit structure exhibiting nonionicity in the block segment containing at least one repeating unit structure exhibiting hydrophobicity and at least one repeating unit structure exhibiting nonionicity Was 40 mol%.

  Furthermore, by hydrolyzing the triblock polymer obtained here in a mixed solution of dimethylformamide and sodium hydroxide, ethyl 4- (2-vinyloxy) ethoxybenzoate in the C block component is hydrolyzed to produce sodium. A salified triblock polymer was obtained. The compound was identified using NMR and GPC.

  Further, a triblock polymer, poly [(IBVE-r-VEEEtPhPh) 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. ) -B- (VEEtPhPh-r-MOVE) -b-VEEtPhCOOH]]. The compound was identified using NMR and GPC.

  In addition, polymerization was carried out by replacing the addition amounts of the B block components VEEtPhPh and MOVE with 1.5 mmol / 1.0 mmol instead of 1.25 mmol / 1.25 mmol, 0.5 mmol / 4.5 mmol (VEEEtPhPh / MOVE). . Other synthesis conditions are the same as described above. The compound was identified by GPC and NMR. As a result, when the addition amount of VEEtPhPh and MOVE is 1.25 mmol / 1.25 mmol, Mn = 21900, Mw / Mn = 1.32, 0.5 mmol / 4.5 mmol, Mn = 26300, Mw / Mn = 1.36. The polymerization ratios were A: B: C = 100: 50: 10 and A: B: C = 100: 100: 10 in this order. The polymerization ratio of the two types of monomers in the B block was 25/25 and 10/90 in order (VEEtPhPh / MOVE). That is, the content of at least one repeating unit structure exhibiting nonionicity in the B block was 50 mol% and 90 mol% in this order.

Example 2
26 parts by mass of each of the three block polymer compounds obtained in Example 1 and 10 parts by mass of a fat-soluble dye oil blue N (same as the trade name, manufactured by Aldrich) were co-dissolved in dimethylformamide, and 400 parts by mass of distilled water. Each was converted into an aqueous phase using an ink part to obtain an ink composition. 0.1 ml of 0.1N sodium hydroxide aqueous solution was added thereto, and the mixture was further left in an ultrasonic homogenizer for 10 minutes for 1 hour. The pH of all the pH test papers was 12. All of these dispersions were very transparent and had a blue color. Although left for 10 days, the fat-soluble dye did not separate and precipitate.

The average particle diameter d and dispersity index μ / G ² of the dispersed particles in the dye dispersion composition obtained by the above method were measured using a dynamic light scattering device (DLS-7000, manufactured by Otsuka Electronics Co., Ltd.). . In order not to change the pH, the measurement was performed by diluting 100 times with an aqueous sodium hydroxide solution having the same concentration. When measured using a dynamic light scattering device (DLS-7000, manufactured by Otsuka Electronics Co., Ltd.), the polymerization ratio of the two monomers in the B block is 30/20, 25/25, 10/90 (VEEEPhPh / MOVE). ) In the order of the block polymer compound (ie, the content of at least one repeating unit structure exhibiting nonionicity in the B block is 40 mol%, 50 mol%, 90 mol% in this order), the average particle size is 83.4 nm, 87.0 nm, 93.8 nm, and dispersion index μ / G ² were 0.08, 0.08, and 0.09.

Comparative Example 1
A dispersion ink was prepared in the same manner as in Example 2, using styrene and an ethylene oxide diblock copolymer (number average molecular weight 10600, number average molecular weight ratio 36:70) and oil blue N as a fat-soluble dye. A strong white turbidity was observed although it had a blue color. The average particle diameter d was 312 nm, and the dispersion index μ / G ² was 0.9. When left for 10 days, a part of the fat-soluble dye separated and precipitated.

Example 3
The ink composition obtained in Example 2 was filled in a print head of an ink jet printer (BJF800, manufactured by Canon Inc.), and a 100 mm × 100 mm square was printed on plain paper with a solid. The show-through at that time was evaluated according to the following criteria.
A: No show-through of the printed image was observed.
○: The ratio of show-through is less than 5% with respect to the entire square image of 100 mm × 100 mm.
Δ: The percentage of show-through is 5% or more and less than 30% with respect to a 100 mm × 100 mm square whole image.
X: The ratio of show-through to the entire square image of 100 mm × 100 mm is 30% to 100%.

  When the ink composition obtained in Example 2 was evaluated, a block polymer compound having a polymerization ratio of 30/20, 25/25, 10/90 (VEEEPhPh / MOVE) of the two monomers in the B block was evaluated. The evaluation results were ◎, 、, and ◎ in order (that is, the content of at least one repeating unit structure exhibiting nonionicity in the B block was 40 mol%, 50 mol%, and 90 mol% in that order).

Comparative Example 2
Using the ink composition prepared by selecting Oil Blue N as the fat-soluble dye in Comparative Example 1, the show-through was evaluated. The ink was filled in a print head of an ink jet printer (BJF800, manufactured by Canon Inc.) and recorded on plain paper using the ink jet printer. Evaluation criteria were the same as in Example 3. As a result, the evaluation result was x.

Example 4
The ink composition obtained in Example 2 was filled in a print head of an ink jet printer (BJF800, manufactured by Canon Inc.), and a 100 mm × 100 mm square was printed on plain paper with a solid. Thereafter, the printed matter was immersed in water for 10 seconds, and the printed image was evaluated for water resistance according to the following criteria.
A: No blur is observed in the image.
○: The blur ratio is less than 5% with respect to the entire square image of 100 mm × 100 mm.
(Triangle | delta): The ratio of a bleeding is 5% or more and less than 30% with respect to a 100 mm x 100 mm square whole image.
X: The ratio of bleeding is 30% or more and 100% or less with respect to the entire square image of 100 mm × 100 mm.

  When the ink composition obtained in Example 2 was evaluated, a block polymer compound having a polymerization ratio of 30/20, 25/25, 10/90 (VEEEPhPh / MOVE) of the two monomers in the B block was evaluated. The evaluation results were ◎, 、, and ◎ in order (that is, the content of at least one repeating unit structure exhibiting nonionicity in the B block was 40 mol%, 50 mol%, and 90 mol% in that order).

Comparative Example 3
Water resistance was evaluated using the ink composition prepared by selecting Oil Blue N as the fat-soluble dye in Comparative Example 1. The ink was filled in a print head of an ink jet printer (BJF800, manufactured by Canon Inc.) and recorded on plain paper using the ink jet printer. Evaluation criteria were the same as in Example 3. As a result, the evaluation result was x.

Example 5
The ink composition obtained in Example 2 was filled in a print head of an ink jet printer (BJF800, manufactured by Canon Inc.), and a 50 mm × 50 mm square was continuously printed with a solid for 3 minutes. Thereafter, the sample was allowed to stand for 10 minutes without a cap or the like, and when a 50 mm × 50 mm square was printed again with a solid, the ratio of blurring or chipping of the image was evaluated according to the following criteria.
(Double-circle): It is completely faint and there is no chipping.
A: The ratio of blurring and chipping is less than 5% with respect to the entire square image of 50 mm × 50 mm.
(Triangle | delta): The ratio of a blur and a chip | tip with respect to the square whole image of 50 mm x 50 mm is 5% or more and less than 30%.
×: The ratio of blurring and chipping is 30% or more and 100 or less with respect to the entire square image of 50 mm × 50 mm.

  When the ink composition obtained in Example 2 was evaluated, a block polymer compound having a polymerization ratio of 30/20, 25/25, 10/90 (VEEEPhPh / MOVE) of the two monomers in the B block was evaluated. The evaluation results were ○, ◎, and ◎ in order (ie, the content of at least one repeating unit structure showing nonionicity in the B block was 40 mol%, 50 mol%, and 90 mol% in order).

Example 6
Instead of the A component monomer and the B component VEEtPhPh in the three types of block polymer compounds synthesized in Example 1, it exhibits hydrophilicity at 20 ° C. or less and is hydrophobic at a temperature higher than 20 ° C. (the upper temperature limit for hydration). Each of the compounds was synthesized using equimolar amounts of 2-ethoxyethyl vinyl ether (EOVE) exhibiting properties. The synthesized compound was identified by GPC and NMR.

  Containing at least one repeating unit structure exhibiting nonionic properties in the B block in the order of the polymerization ratio of the two monomers in the B block of 30/20, 25/25, 10/90 (VEEEtPhPh / EOVE) The amounts were 40 mol%, 50 mol%, and 90 mol% in this order, respectively, and Mn = 2700, 23800, 28000, and Mw / Mn = 1.38, 1.36, 1.34, respectively. The polymerization ratios were A: B: C = 100: 50: 10, A: B: C = 100: 50: 10, and A: B: C = 100: 100: 10 in this order.

  In addition, 26 parts by mass of the obtained triblock polymer and 10 parts by mass of a fat-soluble dye oil blue N (same brand name, manufactured by Aldrich) were co-dissolved in dimethylformamide, respectively, and the aqueous phase was obtained using 400 parts by mass of distilled water. Conversion was performed to obtain an ink composition. After standing for 10 days, oil blue was not separated and precipitated in all the ink compositions.

  In addition, each of the dye dispersion compositions was cooled to 10 ° C., the polymer micelles were disintegrated, and the polymer was dissolved in water. As a result, the dye and the dye solution were separated in all the dye dispersion compositions. It became colorless. This confirmed that the color material was included.

Example 7
<2- (4-methylbenzeneoxy) ethyl vinyl ether (TolOVE: A block), 2- (4-methylbenzeneoxy) ethyl vinyl ether and diethylene glycol methyl vinyl ether (TolOVE-r-MOEOVE: B block), 4- ( Synthesis of triblock polymer poly [TolOVE-b- (TolOVE-r-MOEOVE) -b-VEEEtPhCOOEt]] composed of ethyl 2-vinyloxy) ethoxybenzoate (VEEtPhCOOEt: C block)> (where b is a block polymer) R is a symbol indicating a random polymer).

  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, TolOVE 5.0 mmol (mmol), ethyl acetate 16 mmol, 1-isobutoxyethyl acetate 0.05 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 ethylaluminum 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.

  Subsequently, ToluOVE 1.5 mmol (mmol) and MOEOVE 1.0 mmol toluene solution were added as a B block component, and superposition | polymerization was continued. After confirming the completion of the polymerization of the B block by monitoring using GPC, 5.0 mmol of ethyl 4- (2-vinyloxy) ethoxybenzoate was added as a C block component, and the polymerization was continued. After 3 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 0.6 mol / L 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 = 24100 and Mw / Mn = 1.27. The polymerization ratio was A: B: C = 100: 50: 10. The polymerization ratio of the two types of monomers in the B block was 30:20. That is, the content of at least one repeating unit structure exhibiting nonionicity in the block segment containing at least one repeating unit structure exhibiting hydrophobicity and at least one repeating unit structure exhibiting nonionicity Was 40 mol%.

  Furthermore, by hydrolyzing the triblock polymer obtained here in a mixed solution of dimethylformamide and sodium hydroxide, ethyl 4- (2-vinyloxy) ethoxybenzoate in the C block component is hydrolyzed to produce sodium. A salified triblock polymer was obtained. The compound was identified using NMR and GPC.

  Furthermore, a triblock polymer, poly [TolOVE-b- (TolOVE) 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-MOEOVE) -b-VEEtPhCOOH]]. The compound was identified using NMR and GPC.

  In addition, polymerization was performed by replacing the addition amount of TolOVE and MOEOVE of the B block component with 1.5 mmol / 1.0 mmol instead of 1.25 mmol / 1.25 mmol and 0.5 mmol / 4.5 mmol (TolOVE / MOEOVE). . Other synthesis conditions are the same as described above. The compound was identified by GPC and NMR. As a result, when the addition amount of TolOVE and MOEOVE is 1.25 mmol / 1.25 mmol, Mn = 24600, Mw / Mn = 1.25, 0.5 mmol / 4.5 mmol, Mn = 31500, Mw / Mn = 1.28. The polymerization ratios were A: B: C = 100: 50: 10 and A: B: C = 100: 100: 10 in this order. The polymerization ratio of the two types of monomers in the B block was 25/25 and 10/90 in order (TolOVE / MOEOVE).

Example 8
26 parts by mass of each of the three types of block polymer compounds obtained in Example 7 and 10 parts by mass of a fat-soluble dye oil blue N (same as the trade name, manufactured by Aldrich) were co-dissolved in dimethylformamide, and 400 parts by mass of distilled water. Each was converted into an aqueous phase using an ink part to obtain an ink composition. 0.1 ml of 0.1N sodium hydroxide aqueous solution was added thereto, and the mixture was further left in an ultrasonic homogenizer for 10 minutes for 1 hour. The pH of all the pH test papers was 12. All of these dispersions were very transparent and had a blue color. Although left for 10 days, the fat-soluble dye did not separate and precipitate.

The average particle diameter d and dispersity index μ / G ² of the dispersed particles in the dye dispersion composition obtained by the above method were measured using a dynamic light scattering device (DLS-7000, manufactured by Otsuka Electronics Co., Ltd.). . In order not to change the pH, the measurement was performed by diluting 100 times with an aqueous sodium hydroxide solution having the same concentration. When measured using a dynamic light scattering apparatus (DLS-7000, manufactured by Otsuka Electronics Co., Ltd.), the polymerization ratio of the two monomers in the B block is 30/20, 25/25, 10/90 (TolOVE / MOEOVE). ) In the order of the block polymer compound (that is, the content of at least one repeating unit structure showing nonionicity in the B block is 40 mol%, 50 mol%, 90 mol% in this order), the average particle diameter is 81.2 nm, 80.5 nm, 85.0 nm, and dispersity index μ / G ² were 0.08, 0.08, and 0.09.

Example 9
The ink composition obtained in Example 8 was filled in a printing head of an ink jet printer (BJF800, manufactured by Canon Inc.), and a 100 mm × 100 mm square was printed on plain paper with a solid. The show-through at that time was evaluated according to the following criteria.
A: No show-through of the printed image was observed.
○: The ratio of show-through is less than 5% with respect to the entire square image of 100 mm × 100 mm.
Δ: The percentage of show-through is 5% or more and less than 30% with respect to a 100 mm × 100 mm square whole image.
X: The ratio of show-through to the entire square image of 100 mm × 100 mm is 30% to 100%.

  When the ink composition obtained in Example 8 was evaluated, the block polymer compound having a polymerization ratio of 30/20, 25/25, 10/90 (TolOVE / MOEOVE) of the two monomers in the B block was evaluated. The evaluation results were ◎, 、, and ◎ in order (that is, the content of at least one repeating unit structure exhibiting nonionicity in the B block was 40 mol%, 50 mol%, and 90 mol% in that order).

Example 10
Example 8 The obtained ink composition was filled in a print head of an inkjet printer (BJF800, manufactured by Canon Inc.), and a 100 mm × 100 mm square was printed on plain paper with a solid. Thereafter, the printed matter was immersed in water for 10 seconds, and the printed image was evaluated for water resistance according to the following criteria.
A: No blur is observed in the image. O: The blur ratio is less than 5% with respect to the entire square image of 100 mm × 100 mm.
(Triangle | delta): The ratio of a bleeding is 5% or more and less than 30% with respect to a 100 mm x 100 mm square whole image.
X: The ratio of bleeding is 30% or more and 100% or less with respect to the entire square image of 100 mm × 100 mm.

  When the ink composition obtained in Example 8 was evaluated, the block polymer compound having a polymerization ratio of 30/20, 25/25, 10/90 (TolOVE / MOEOVE) of the two monomers in the B block was evaluated. The evaluation results were ◎, 、, and ◎ in order (that is, the content of at least one repeating unit structure exhibiting nonionicity in the B block was 40 mol%, 50 mol%, and 90 mol% in that order).

Example 11
Each of the ink compositions obtained in Example 8 was filled in a print head of an ink jet printer (BJF800, manufactured by Canon Inc.), and a 50 mm × 50 mm square was continuously printed with a solid for 3 minutes. Thereafter, the sample was allowed to stand for 10 minutes without a cap or the like, and when a 50 mm × 50 mm square was printed again with a solid, the ratio of blurring or chipping of the image was evaluated according to the following criteria.
(Double-circle): It is completely faint and there is no chipping.
A: The ratio of blurring and chipping is less than 5% with respect to the entire square image of 50 mm × 50 mm.
(Triangle | delta): The ratio of a blur and a chip | tip with respect to the square whole image of 50 mm x 50 mm is 5% or more and less than 30%.
×: The ratio of blurring and chipping is 30% or more and 100 or less with respect to the entire square image of 50 mm × 50 mm.

  When the ink composition obtained in Example 8 was evaluated, the block polymer compound having a polymerization ratio of 30/20, 25/25, 10/90 (TolOVE / MOEOVE) of the two monomers in the B block was evaluated. The evaluation results were ○, ◎, and ◎ in order (ie, the content of at least one repeating unit structure showing nonionicity in the B block was 40 mol%, 50 mol%, and 90 mol% in order).

Example 12
Instead of the monomer of component A and the TolOVE of component B in the three types of block polymer compounds synthesized in Example 7, it exhibits hydrophilicity at 20 ° C. or less and is hydrophobic at a temperature higher than 20 ° C. (the upper limit temperature for hydration). Each of the compounds was synthesized using equimolar amounts of 2-ethoxyethyl vinyl ether (EOVE) exhibiting properties. The synthesized compound was identified by GPC and NMR. Containing at least one repeating unit structure exhibiting nonionic properties in the order of the polymerization ratio of the two monomers in the B block of 30/20, 25/25, 10/90 (EOOVE / MOEOVE) The amounts were 40 mol%, 50 mol%, and 90 mol% in this order, respectively, with Mn = 18100, 18600, 27900, and Mw / Mn = 1.32, 1.30, 1.35, respectively. The polymerization ratios were A: B: C = 100: 50: 10, A: B: C = 100: 50: 10, and A: B: C = 100: 100: 10 in this order.

  In addition, 26 parts by mass of the obtained triblock polymer and 10 parts by mass of a fat-soluble dye oil blue N (same product name, manufactured by Aldrich) were co-dissolved in dimethylformamide, respectively, and converted into an aqueous phase using 400 parts by mass of distilled water. An ink composition was obtained. After standing for 10 days, oil blue was not separated and precipitated in all the ink compositions.

  In addition, each of the dye dispersion compositions was cooled to 10 ° C., the polymer micelles were disintegrated, and the polymer was dissolved in water. As a result, the dye and the dye solution were separated in all the dye dispersion compositions. It became colorless. This confirmed that the color material was included.

  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 is an ink jet recording method in which show-through is suppressed when printed on a recording medium, water resistance is improved, and dispersibility stability of a functional substance such as a pigment or dye in a solvent is good. It can be used for a recording device.

1 is a diagram showing a schematic mechanism of an image recording apparatus of the present 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 (17)

  A block polymer compound having at least two or more block segments, wherein at least one block segment of the block polymer compound exhibits hydrophobicity, and has at least hydrophilic property and nonionic property A block polymer compound containing one type of repeating unit structure.   The block polymer compound according to claim 1, wherein the block polymer compound is amphiphilic.   The block polymer compound according to claim 1 or 2, wherein the block polymer compound contains a block segment exhibiting hydrophobicity and a block segment exhibiting hydrophilicity.   The block polymer compound according to any one of claims 1 to 3, wherein the block polymer compound has three or more block segments.   The block polymer compound according to any one of claims 1 to 4, which contains a polyalkenyl ether structure as a repeating unit structure.   The block polymer compound according to any one of claims 1 to 5, comprising a polyvinyl ether structure as a repeating unit structure. The repeating unit structure exhibiting hydrophobicity is represented by the following general formula (1), and the repeating unit structure exhibiting hydrophilicity and nonionic is a repeating unit represented by the following general formula (2): Item 7. The block polymer compound according to any one of Items 1 to 6.

Wherein R ¹ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, Ph, Pyr, Ph-Ph, Ph-Pyr, — (CH (R ² ) —CH (R ³ ) -O) _p -R ⁴ and _{- (CH 2) m - (} O) is selected from _n -R ^4, hydrogen atoms in the aromatic ring is a linear or branched alkyl group having 1 to 4 carbon atoms And a carbon atom in the aromatic ring may be substituted with a nitrogen atom, p is an integer of 1 to 18, m is an integer of 1 to 36, and n is 0 or 1. R ² , R ³ is each independently a hydrogen atom or CH _3. R ⁴ is a linear, branched or cyclic alkyl group having 4 to 18 carbon atoms, Ph, Pyr, Ph-Ph, Ph-Pyr, -CHO, -CO-CH = CH ₂ or _{-CO-C (CH 3) =} CH 2, a -CH ₂ COOR ^5, carbon atoms The bonded hydrogen atom may be a linear or branched alkyl group having 1 to 4 carbon atoms or F, Cl or Br, and the carbon atom in the aromatic ring may be substituted with a nitrogen atom. R ⁴ is a linear, branched or cyclic alkyl group having 3 carbon atoms, p is an integer of 1 to 3, and a hydrogen atom bonded to a carbon atom is a straight chain having 1 to 4 carbon atoms. A chain or branched alkyl group or F, Cl, Br, and a carbon atom in the aromatic ring may be substituted with a nitrogen atom, and R ⁵ is an alkyl group having 1 to 4 carbon atoms. -Ph represents a phenyl group, -Pyr represents a pyridyl group, -Ph-Ph represents a biphenyl group, and -Ph-Pyr represents a pyridylphenyl group, and the pyridyl group, biphenyl group, and pyridylphenyl group are positional isomers. May be good.)

Wherein R ⁶ is selected from a hydrogen atom or — (CH (R ⁷ ) —CH (R ⁸ ) —O) _p —R ⁹ and — (CH ₂ ) _m — (O) _n —R ^9. Is an integer from 1 to 18, m is an integer from 1 to 36, and n is 0 or 1. R ⁷ and R ⁸ are each independently a hydrogen atom or —CH ₃ , R ⁹ is a hydrogen atom and has 1 carbon atom. Represents a linear, branched or cyclic alkyl group from 1 to 2, R ⁹ is a linear, branched or cyclic alkyl group having 3 carbon atoms, and p is an integer of 4 to 18. )   At least one type of repeating unit structure showing nonionicity in the block segment containing at least one type of repeating unit structure showing hydrophobicity and at least one type of repeating unit structure showing hydrophilicity and nonionicity The block polymer compound according to any one of claims 1 to 7, wherein the content of is at least 50 mol%.   A polymer-containing composition comprising the block polymer compound according to any one of claims 1 to 8, a solvent or dispersion medium, and a functional substance.   The polymer-containing composition according to claim 9, wherein the functional substance is included in the block polymer compound.   The polymer-containing composition according to claim 9 or 10, wherein the functional substance is a color material.   An ink composition comprising the polymer-containing composition according to claim 9.   The ink composition according to claim 12, wherein the ink composition is an inkjet ink composition.   A liquid application method comprising using the ink composition according to claim 12.   14. A liquid application method in which ink is ejected from an ink ejection unit and applied onto a recording medium for recording, wherein the ink is the ink composition according to claim 12 or 13.   The liquid application method according to claim 15, wherein the ink is ejected from the ink ejection unit by applying thermal energy to the ink.   The liquid application apparatus used for the liquid application method of any one of Claims 14 thru | or 16.

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