JP2005280352A - Image forming method using liquid composition, pattern forming method and liquid applying device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form an excellent image on a medium to be recorded. <P>SOLUTION: In the image forming method by which two or more kinds of liquid composition are applied on a medium to be recorded to form an image on the medium to be recorded, at least a first liquid composition including a function substance, an anionic amphiphilic polymer and a liquid medium, and also a second liquid composition including a function substance, a multi-valent cation, an anionic amphiphilic polymer and a liquid medium are contained. The method comprises a process of preparing a plurality of liquid compositions in which at least either one of the polymers of the first liquid composition or the second liquid composition is a block polymer or a graft polymer, and a process in which the first liquid composition and the second liquid composition are applied on the medium to be recorded to bring both compositions into contact with each other, allowing at least one of the liquid components to increase viscosity. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an image forming method, a pattern forming method, and a liquid applying apparatus that suppresses the occurrence of bleeding due to contact between liquid compositions containing a functional substance and has good fixability of the functional substance on a medium.

  In aqueous dispersion materials containing functional substances, conventionally, functional materials such as herbicides, pesticides such as insecticides, anticancer agents, antiallergic agents, anti-allergic agents, etc., and inks and toners with colorants Coloring materials such as these 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. On the other hand, there is an active movement to use these image forming technologies for forming devices such as semiconductor elements and display elements, and they are being developed widely not only for image formation but also for industrial use.

  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.

As the ink used in these methods, since an aqueous dye solution is usually used, bleeding occurs when colors are superimposed, or a phenomenon called feathering appears in the recording fiber on the recording medium in the fiber direction of the paper. There was a case. In addition, since dyes are mainly used as coloring materials, improvement in weather resistance is also strongly demanded. There is also an example in which a reaction between a dye ink and a pigment ink is used for the purpose of improving these (Patent Document 1). There is also an example using a reactive self-dispersing pigment (Patent Document 2). However, many improvements are still desired.
US Pat. No. 5,320,668 US Pat. No. 6,281,267

  The present invention has been made in view of such a background art, and a liquid composition containing two or more kinds of liquid compositions containing functional substances and contacting the liquid compositions is used. An object of the present invention is to provide a method for forming a good image or pattern on a recording medium by increasing the viscosity of the object.

  Further, the present invention makes it possible to suppress the mixing of the functional substance on the medium by using the method for forming an image on the recording medium, and to obtain a good fixing property in the recording part. An object of the present invention is to provide a good pattern forming method.

  Another object of the present invention is to provide a liquid applicator used in a good pattern forming method using a method for recording on such a recording medium.

  The image forming method provided by the present invention is an image forming method in which two or more liquid compositions are applied onto a recording medium to form an image on the recording medium. A second liquid composition containing a first liquid composition containing a liquid polymer, a liquid medium, a functional substance, a polyvalent cation, an anionic amphiphilic polymer, and a liquid medium A plurality of liquid compositions in which at least one of the polymers of the first liquid composition and the second liquid composition is a block polymer or a graft polymer, and the first liquid composition And the second liquid composition are applied onto the recording medium, the first liquid composition and the second liquid composition are brought into contact with each other, and at least one of these liquid compositions is increased. A process of producing viscosity and It is characterized in that it has a.

In the present invention, the polyvalent cation of the second liquid composition can be a metal cation.
Moreover, both the polymers in the first and second liquid compositions can be block polymers.

Furthermore, the present invention includes an embodiment in which the functional substance is encapsulated by the amphiphilic polymer.
Moreover, this invention includes the aspect whose pKa of the organic acid formed by proton-adding the anion of the anionic amphiphilic polymer of the second composition to 2 or less.

The organic acid may be a halogen-substituted benzoic acid group or a sulfonic acid group.
Moreover, this invention includes the aspect in which the anionic amphiphilic polymer of a 2nd composition contains a dioxyethylene unit structure.

In the present invention, the anion of the amphiphilic polymer of the first liquid composition can be a carboxylate anion.
Moreover, this invention includes the aspect in which the said amphiphilic polymer has the repeating structure of the monomer unit which consists of alkenyl ether.
The functional substance can also be a color material.

  The pattern forming method provided by the present invention is a method for forming a pattern comprising a functional substance-attached region by applying a liquid composition containing a functional substance to a pattern forming medium, the functional substance comprising: And a first liquid composition containing an anionic amphiphilic polymer and a liquid medium, a functional substance, a polyvalent cation, an anionic amphiphilic polymer, and a liquid medium Preparing a plurality of liquid compositions, wherein at least one of the first liquid composition and the polymer of the second liquid composition is a block polymer or a graft polymer; The first liquid composition and the second liquid composition are applied onto the pattern forming medium, the first liquid composition and the second liquid composition are brought into contact with each other, and these liquid compositions are brought into contact with each other. At least of things Characterized in that it and a step of causing a thickening towards.

The liquid composition can be applied by an ink jet method.
Further, the liquid application device provided by the present invention includes a first liquid composition containing a functional substance, an anionic amphiphilic polymer, and a liquid medium, a functional substance, a polyvalent cation, At least a second liquid composition containing an anionic amphiphilic polymer and a liquid medium, wherein at least one of the polymers of the first liquid composition and the second liquid composition is a block polymer or In addition to the graft polymer, the first liquid composition and the second liquid composition come into contact with each other, whereby energy is applied to a plurality of liquid compositions in which at least one of these liquid compositions is thickened. It is characterized by comprising liquid applying means for applying the plurality of liquid compositions onto a recording medium, and driving means for driving the liquid applying means.

  The present invention uses a liquid composition containing two or more kinds of functional substances and has a viscosity increase when the liquid composition is brought into contact with the liquid composition. It is possible to provide a recording method capable of forming a good image or pattern of a functional substance.

  Further, the present invention makes it possible to suppress the mixing of the functional substance on the medium by using such a method for recording on the recording medium, and it is possible to obtain a good fixing property in the recording part and to obtain a better condition. A pattern forming method can be provided.

  In addition, the present invention can provide a liquid applying apparatus that is used for a good pattern forming method using a method for recording on such a recording medium.

Hereinafter, the present invention will be described in detail.
The image forming method of the present invention is a method for forming an image on a recording medium by applying two or more liquid compositions onto the recording medium. A first liquid composition containing a polymer, a liquid medium, a functional substance, a polyvalent cation, an anionic amphiphilic polymer, and a second liquid composition containing a liquid medium Preparing a plurality of liquid compositions comprising at least one of the first liquid composition and the polymer of the second liquid composition being a block polymer or a graft polymer; and the first liquid composition and the A second liquid composition is applied onto the recording medium, the first liquid composition and the second liquid composition are brought into contact with each other, and thickening occurs in at least one of these liquid compositions. And having a process of And it features.

  In the method for forming an image on the recording medium according to the present invention, a combination of two liquid compositions in which thickening occurs at the contact portion of at least one liquid composition when contacting with each other. Can be adopted. Furthermore, two or more kinds of liquid compositions in such a combination may be included. For example, when the liquid composition is composed of three kinds of liquid compositions, the first liquid composition and the second liquid composition constitute a combination showing the above relationship, and the second liquid composition and the third liquid composition The thing in which the thing comprises the combination which satisfy | fills said relationship can be illustrated.

Each liquid composition has a configuration in which a functional substance and an amphiphilic polymer are contained in a liquid medium.
The functional substance according to the present invention means a compound or composition that exhibits a desired function. For example, agrochemicals such as herbicides and insecticides, pharmaceuticals such as anticancer agents, antiallergic agents and anti-inflammatory agents, and coloring materials, typically pigments or dyes, can be mentioned. For example, if it is said agricultural chemical, it is an active compound which has a herbicidal effect, and an active compound which has an insecticidal effect. Moreover, if it is said pharmaceutical, it is a compound which relieves or relieves the symptom of object. In the present invention, it is possible to facilitate the expression of the function by improving the fixability to a place where the function is exerted and the place selectivity.

In the present invention, it is particularly effective when the functional substance is a color material. Examples of the color material include granular solids such as pigments and dye compounds.
As described above, examples of the color material include pigments, and examples include inorganic achromatic pigments, organic and inorganic chromatic pigments, and colorless or light color pigments, metallic luster pigments, and the like. For the present invention, a newly synthesized pigment may be used. An example is given below.

  Examples of black pigments include Raven 1060, Raven 1080, Raven 1170 (above, Columbian Carbon), Black Pearls L, MOGUL-L, Regal 400R (above, Cabot), Color Black FW1, Color Black FW2, Black FW200 (manufactured by Degussa Co., Ltd.), 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, but is not limited thereto.

  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 and the like, but are not limited thereto.

  Examples of yellow pigments include C.I. I. Pigment Yellow-12, 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 and the like, but are not limited thereto.

  In the present invention, a dye can be used in the same manner as the pigment. Dyes that can be used may be known or new ones. For example, direct dyes, acidic dyes, basic dyes, reactive dyes, water-soluble dyes for food coloring, and fat-soluble (oil-soluble) as described below. A dye or an insoluble pigment of a disperse dye can be used, but it may be used in a solid state. In this respect, for example, oil-soluble dyes may be used. Examples include C.I. I. Solvent Blue, -33, -38; C.I. I. Solvent Red, −25, −31; C.I. I. Solvent yellow, -1, -49 etc. are mentioned.

  Water-soluble dyes can also be used. I. Direct black, -17, -19, -22; I. Direct yellow, -12, -24, -26; I. Direct red, -1, -4, -13; I. Direct blue, -6, -22, -25; I. Direct orange, -34, -39; C.I. I. Direct violet, -47; I. Direct Brown, -109; C.I. I. Direct dyes such as direct green and -59, C.I. I. Acid Black, -2; C.I. I. Acid Yellow, -11, -17; C.I. I. Acid Red, -1, -6; C.I. I. Acid Blue, -9, -22; C.I. I. Acid Orange, -7, -19; C.I. I. Acid violet, acidic dyes such as -49, C.I. I. Reactive Black, -1, -5; C.I. I. Reactive Yellow, -2, -3; C.I. I. Reactive red, -3, -13, -16, -21; I. Reactive blue, -2, -3, -5; I. Reactive orange, -5, -7; C.I. I. Reactive violet, -1, -4; C.I. I. Reactive Green, -5, -8; C.I. I. Reactive brown, reactive dyes such as -2; C.I. I. B. Basic Black, -2; I. B. basic red, -1, -2, -9, -12, -13, -14, -27; I. B. basic blue, -1, -3, -5, -7, -9, -24, -25, -26, -28, -29; I. B. basic violet, -7, -14, -27; I. Food black, -1, -2, etc. are mentioned.

Moreover, as oil-soluble dye, the commercial item of each color is illustrated below.
Examples of black oil-soluble dyes include C.I. I. Solvent Black-3, -22: 1, -50, etc. are mentioned, but it is not limited to these.

Examples of yellow oil-soluble dyes include C.I. I. Solvent Yellow-1, -25: 1, -172 etc. are mentioned, However, It is not limited to these.
Examples of orange oil-soluble dyes include C.I. I. Solvent Orange-1, -40: 1, -99 etc. are mentioned, However, It is not limited to these.

Examples of red oil-soluble dyes include C.I. I. Solvent Red-1, -111, -229, etc. are mentioned, but it is not limited to these.
Violet oil-soluble dyes include C.I. I. Solvent Violet-2, -11, -47 etc. are mentioned, However, It is not limited to these.

Examples of blue oil-soluble dyes include C.I. I. Solvent Blue-2, -43, -134 etc. are mentioned, However, It is not limited to these.
Green oil-soluble dyes include C.I. I. Solvent Green-1, -20, -33 etc. are mentioned, However, It is not limited to these.

Examples of brown oil-soluble dyes include C.I. I. Solvent Brown-1, -12, -58 etc. are mentioned, However, It is not limited to these.
In addition, although the example of these said coloring material is especially preferable with respect to the composition of this invention, the coloring material used for this invention is not specifically limited to the said coloring material.

  The functional substance is preferably contained in the range of 0.01 to 80% by mass with respect to the total mass of the liquid composition. When two or more kinds of functional substances are used, it is preferable to set the total amount within this range. When the amount of the functional substance is less than 0.01% by mass, a sufficient function may not be obtained, and when it exceeds 80% by mass, the dispersibility may be deteriorated. A preferable range is from 0.1% by mass to 50% by mass. More preferably, it is the range of 0.3 mass% to 30 mass%.

  The liquid composition in the present invention contains a liquid medium. Although the liquid medium contained in the liquid composition of this invention is not specifically limited, The liquid medium which can melt | dissolve, suspend, or disperse | distribute the component contained in a liquid composition is meant. In the present invention, various water-soluble organic solvents such as linear, branched and cyclic aliphatic hydrocarbons, aromatic hydrocarbons and heteroaromatic hydrocarbons, water-soluble organic solvents, water and the like can be used as the liquid medium. Of course, it is also possible to use those mixed solvents.

  In particular, in the liquid composition of the present invention, water or an aqueous liquid medium composed of water and a water-soluble organic solvent can be preferably used. Examples of water-soluble organic solvents include, for example, 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 Examples thereof include polyhydric alcohol ethers such as monobutyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether, and nitrogen-containing solvents such as N-methyl-2-pyrrolidone, substituted pyrrolidone and triethanolamine. Moreover, monohydric alcohols, such as methanol, ethanol, isopropyl alcohol, can also be used, and it can be used in combination of 2 or more types as needed.

  The pH of the aqueous liquid medium can be used in the whole range, but preferably the pH is between 1 and 14. The content of the liquid medium contained in the liquid composition used in the present invention can be selected from a range of 0.9% by mass to 99% by mass, and preferably 10% by mass to 99% by mass. When the amount is less than 0.9% by mass, the viscosity of the composition may be too high. When the amount exceeds 99% by mass, the function of the functional substance may not be exhibited sufficiently.

  In addition, as the amphiphilic polymer used in the liquid composition in the present invention, a block polymer or a graft polymer is used, and two or more amphiphilic polymers are combined in the same liquid composition as necessary. You can also. The block polymer referred to in the present invention is a copolymer in which polymer units having different repeating unit structures, that is, block segments, are connected by covalent bonds, and is also referred to as a block copolymer or a block copolymer.

  The present invention is characterized by the use of an amphiphilic polymer. Amphiphilicity refers to the property of having both an amphiphilic site and a lyophobic site. For example, when the medium is water, the amphiphile forms micelle particles and the particles can be observed.

  The block polymer is a polymer called a block polymer or a block copolymer or a block copolymer in which polymers having different segment structures are covalently bonded to one chain. The graft polymer used in the present invention is a polymer in which two polymer chains are linked in a branch shape. For example, when the trunk and the branch have different amphiphilic properties, the polymer becomes an amphiphilic graft polymer. Also called graft copolymer or graft copolymer. Typically, it is a polymer in which polymers having different segment structures are covalently bonded in a T-shape.

  Next, the block polymer which is a component used more characteristically in the present invention will be described. Specific examples of the block polymer 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 blocks. A conventionally known block polymer such as a block polymer having γ can also be used. In the present invention, the block polymer is more preferably a block form such as AB, ABA, ABD. A, B, and D indicate different block segments. An ABD block polymer is preferable in that it can form a good encapsulated state, and an ABD block polymer in which hydrophobic, hydrophilic, and hydrophilic block segments are formed in the order of ABD is more preferable. Of the hydrophilicity and hydrophilicity, B is preferably nonionic hydrophilic and D is preferably ionic hydrophilic.

  Moreover, in this invention, it may couple | bond with the polymer chain with a block polymer in T shape, and may become a graft polymer. Each segment of the block polymer may be a copolymer segment, and the form of the copolymer is not limited. For example, the segment may be a random segment or a gradient segment.

In the present invention, a block polymer containing a polyalkenyl ether structure is preferably used. Particularly preferred is a block polymer containing a polyvinyl ether structure. A number of methods for synthesizing block polymers containing a polyalkenyl ether structure preferably used in the present invention have been reported (for example, JP-A-11-080221), but a method by cationic living polymerization by Aoshima et al. 1986, page 417, JP-A-11-322942, JP-A-11-322866). By conducting polymer synthesis by cationic living polymerization, various polymers such as homopolymers and copolymers composed of two or more monomers, as well as block polymers, graft polymers, and gradient polymers, can be lengthened (molecular weight). It can be accurately aligned and synthesized. Polyalkenyl ether can introduce various functional groups into its side chain. 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 containing a polyalkenyl ether structure may be a copolymer composed of vinyl ether and another polymer. Preferably, a polymer having a polyvinyl ether repeating unit structure is used.

  An example of the repeating unit structure of a block polymer containing a polyvinyl ether structure is represented by the following general formula (1).

[Wherein 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) _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 , and when R ₄ is other than a hydrogen atom, the hydrogen atom on the carbon atom is a straight chain having 1 to 4 carbon atoms Alternatively, a branched alkyl group or F, Cl, Br, and a carbon atom in the aromatic ring can be substituted with a nitrogen atom, respectively. R ₅ is H or an alkyl group having 1 to 5 carbon atoms. ]

  In the above, -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.

The repeating unit structure represented by the general formula (1) is preferably used in the A or B segment of the ABD triblock polymer preferably used in the present invention.
Specific examples of the repeating unit structure represented by the general formula (1) used include the following.

In general formula (1) represented by the repeating unit structure - show a structure of only -OR ₁ group of the side chain attached to the below - (CH ₂ -CH).

(Ph represents a phenylene or phenyl group.)
The amphiphilic block polymer can be obtained, for example, by selecting and synthesizing a hydrophobic block segment and a hydrophilic block segment. In the case of a graft polymer, for example, an amphiphilic polymer can be obtained by grafting a hydrophobic polymer segment to a hydrophilic polymer.

Next, an example of a repeating unit structure having a functional group in the form of an organic acid or a salt of an organic acid used characteristically in the present invention will be described.
Specific examples of the repeating unit structure of polyalkenyl ether suitably used as an anionic segment are given below.

  The repeating unit structure represented by the following general formula (2), (3), (4), (5) and (6) is mentioned.

(In the formula, A represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted. M represents an integer of 0 to 30. When m is plural, A independently represents any of the above groups, B represents a single bond or an optionally substituted alkylene group, D represents an aromatic ring structure, n represents an integer of 1 to 10, and n represents In the case of a plurality, each D independently represents the above group, and M represents a monovalent or polyvalent metal cation.)

  Examples of the substituent that the alkylene groups A and B in the general formula (2) can have include an alkyl group. Examples of the aromatic ring structure of D include phenylene and naphthylene.

(In the formula, R represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted. M represents an integer of 0 to 30. When m is plural, R independently represents the above group, q represents an integer of 1 to 30, and M represents a monovalent or polyvalent metal cation.)

Examples of the monovalent metal cation of M in the general formulas (2) and (3) include sodium ion, potassium ion, and lithium ion.
Examples of the polyvalent metal cation of M include divalent cations such as Ca, Cu, Mg, Ni, Zn, Fe, and Co, and trivalent cations such as Al, Nd, Y, Fe, and La. Examples thereof include diammonium cation and triammonium cation.

Next, specific examples of the repeating unit structure represented by the general formula (2) are shown below.
Note that the structure of only the side chain —O (AO) _m B (D) _n COO ⁻ M group bonded to — (CH ₂ —CH) — of the repeating unit structure represented by the general formula (2) It is shown below.

Next, specific examples of the repeating unit structure represented by the general formula (3) are shown below.
In addition, the structure of only the —O (RO) _m (CH ₂ ) _q COO ⁻ M group of the side chain bonded to — (CH ₂ —CH) — of the repeating unit structure represented by the general formula (3) It is shown below.

(Ph represents 1,4-phenylene or 1,3-phenylene. Np represents 2,6-naphthylene, 1,4-naphthylene, or 1,5-naphthylene.)

(In the formula, R ⁴⁰ represents -X- (Y) _t- (COOH) _r , -X- (Y) _t- (COOR ¹⁰ ) _r , -X- (Y) _t- (COO-M) _r . X is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or — (CH (R ⁵ ) —CH (R ⁶ ) —O) _p — (CH ₂ ) _m — (O) _n - or _{- (CH 2) m - (} O) n - (CH 2) q - or .r representing at least one is substituted by an oxygen atom or a carbonyl group or an aromatic ring structure the structure of those of the methylene groups is Represents 1 or 2. p represents an integer from 1 to 20. m represents an integer from 0 to 36. n represents 1 or 0. q represents an integer from 0 to 20. Y represents aromatic. Represents an aromatic ring structure in which at least one hydrogen atom is substituted with a fluorine atom, t represents an integer of 0 to 10. Each Y is optionally different .R ¹⁰ when the number may be substituted, .M represents an alkyl group or an aromatic ring structure represents a monovalent or multivalent cation .R ^5, R ⁶ Represents a hydrogen atom or an alkyl group, and R ⁵ and R ⁶ may be the same or different.)

Specific examples of the repeating unit structure represented by the general formula (4) are given below.
In general formula (4) represented by the repeating unit structure - shows the structure of only the -OR ⁴⁰ group of the side chain attached to the below - (CH ₂ -CH).

(In the formula, R ⁵⁰ represents —X— (Y) _t —SO ₃ H, —X— (Y) _t —SO ₃ R ¹⁰ , —X— (Y) _t —SO ₃ —M. X represents carbon. A linear, branched or cyclic alkylene group of 1 to 20, or — (CH (R ⁵ ) —CH (R ⁶ ) —O) _p — (CH ₂ ) _m — (O) _n — 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, an oxygen atom or an aromatic ring structure, p is 1 to 20 M represents an integer of 0 to 36. n represents 1 or 0. q represents an integer of 0 to 20. Y represents an optionally substituted aromatic ring structure. Represents an integer of 0 to 10. When t is plural, each Y may be different, R ¹⁰ represents an alkyl group, M is monovalent or polyvalent R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group, and R ⁵ and R ⁶ may be the same or different.

Specific examples of the repeating unit structure represented by the general formula (5) are given below.
In general formula (5) represented by the repeating unit structure - shows the structure of only the -OR ⁵⁰ group of the side chain attached to the below - (CH ₂ -CH).

(Ph represents 1,4-phenylene or 1,3-phenylene. Py represents 2,5-pyrimidyl, Pyr represents 2,5-pyridyl. Np represents 2,6-naphthyl or 1,4-naphthyl. Or 1,5-naphthyl.)

(In the formula, A ′ represents an optionally substituted polyalkenyl ether group. B represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted. m represents an integer of 0 to 30. When m is plural, each B may be different, and D is a single bond or a linear or branched substituted group having 1 to 10 carbon atoms. Represents an alkylene group that may be substituted, E represents an aromatic ring that may be substituted, a condensed ring that may be substituted, or a structure in which up to three aromatic rings that may be substituted are bonded by a single bond R ⁶⁰ represents —COOH, —COOR ⁴ , or —COO ⁻ M. R ⁴ represents a hydrogen atom or a linear or branched substituted group having 1 to 5 carbon atoms. Also good alkylene group or substituted .M representing an aromatic ring represents a monovalent or multivalent metal cations. Further, n represents an integer of 2 or more, the R ⁶⁰ groups in the formula is substituted on the aromatic ring of E In addition, a hydrogen atom not substituted with R ⁶⁰ in the aromatic ring may be substituted.)
Specific examples of the repeating unit structure represented by the general formula (6) include the following.

An example in which the amphiphilic polymer of the second ink of the present invention has a dioxyethylene unit structure will be described.
The repeating unit structure having a dioxyethylene unit structure used in the present invention is preferably represented by the following general formula (7).

In the formula, R ₇ is selected from a hydrogen atom or — (CH (R ₈ ) —CH (R ₉ ) —O) _p —R ₁₀ and — (CH ₂ ) _m — (O) _n —R ₁₀ .
p is an integer of 1 to 18, m is an integer of 1 to 36, and n is 0 or 1.

R ₈ and R ₉ are each independently a hydrogen atom or —CH ₃ .
R ₁₀ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms.

  Specific examples of the repeating unit structure having a dioxyethylene structure represented by the general formula (7) are given below, but the invention is not limited thereto.

For the second liquid composition in the present invention, an anionic amphiphilic polymer having a polyvalent cation is used.
In a preferred embodiment of the present invention, the polyvalent cation of the second liquid composition is a metal cation. Specific examples include divalent cations such as Ca, Cu, Mg, Ni, Zn, Fe, and Co, and trivalent cations such as Al, Nd, Y, Fe, and La, and diammonium cations as nonmetallic cations, Although a triammonium cation etc. are mentioned, this invention is not limited to these specific examples.

  As the anionic part of the amphiphilic polymer used in the first liquid composition in the present invention, the carboxylic acid structures of the general formulas (2), (3) and (6) are preferably used. As the anionic portion of the amphiphilic polymer that is a counter ion of the polyvalent cation of the second liquid composition of the present invention, the structures of the general formulas (4) and (5) are preferably used.

  The molecular weight distribution Mw (weight average molecular weight) / Mn (number average molecular weight) of the block polymer used in the present invention is preferably 2.0 or less. More preferably, it is 1.6 or less, More preferably, it is 1.3 or less. More preferably, it is 1.2 or less.

  The number average molecular weight Mn of the block polymer or graft polymer used in the present invention is 200 or more. Preferably it is 3000 or more and should not exceed 1 million. When the number average molecular weight is less than 200, the dispersion stability of the functional substance may not be good. The number average molecular weight and weight average molecular weight of the polymer of the present invention can be measured by volume exclusion chromatography (also known as gel permeation chromatography / GPC).

  The content of the block polymer or graft polymer used in the liquid composition of the present invention is 0.1% by mass or more and 90% by mass or less, preferably 1% by mass or more and 50% by mass, and less than 0.1% by mass. In this case, the dispersion or dissolution state of the functional substance in the liquid composition may not be sufficient, and if it exceeds 90% by mass, the viscosity may become too high.

  It is preferable that the functional substance contained in the liquid composition is included in the block polymer or graft polymer in the sense of suppressing modification due to the influence from the external environment. An amphiphilic block polymer or graft polymer is effective in that a functional substance can be easily included by forming a self-assembled structure. Also, in order to improve dispersion stability and inclusion, it is preferable that the molecular mobility of the block polymer or graft is more flexible because it has a point of being easily entangled and compatible with the surface of the functional substance. .

  Furthermore, as described later in detail, it is preferable that it is flexible also in that a coating layer can be easily formed on a recording medium. 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 has a low glass transition point and flexible properties.

  As described above, the liquid composition of the present invention preferably contains a functional substance. The encapsulated state is formed, for example, by adding a solution obtained by dissolving a coloring material in an organic solvent insoluble in water to micelles in water formed by the block polymer or graft polymer, and then distilling off the organic solvent. I can do it. In addition, from the state where block polymer or graft polymer and coloring material are co-dissolved or uniformly dispersed in an organic solvent, the inclusion state is formed by using a self-integrated process by phase inversion in an aqueous solvent. It is also possible to do. The remaining solvent may be distilled off. Furthermore, the encapsulated state can also be formed by adding a dispersion of a pigment in an organic solvent insoluble in water to micelles in water formed by, for example, a block polymer or a graft polymer. A block polymer is used in both the first liquid composition and the second liquid composition of the present invention in that a self-assembled structure can be formed more suitably and a good state can be formed from the viewpoint of recording characteristics. preferable.

  Confirmation of the inclusion state can be performed by instrumental analysis such as various electron microscopes and X-ray diffraction. In addition, in the case of inclusion in a micelle state, the inclusion state can be indirectly confirmed by separating the coloring material from the solvent separately from the polymer under the micelle collapse condition. As described above, it is preferable that the block polymer or graft polymer forms a micelle state, and for this purpose, an amphiphilic polymer is effective as the block polymer or graft polymer used in the present invention. In this sense, the block polymer or graft polymer preferably has a polymer segment having an ionic repeating unit structure. From the necessity described later, it is preferable to have an ionic repeating unit structure, but it is also preferable for forming an encapsulated state. In the present invention, it is preferable to use a block polymer in view of various properties such as dispersion stability, inclusion of a functional substance, and viscosity.

  The proportion of the functional substance contained in the block polymer or graft polymer with respect to the total amount of the functional substance contained in the liquid composition is preferably 90% by mass or more, more preferably 95% by mass or more, and even 98% by mass. The above is preferable. This quantitative ratio can also be observed by various electron microscopes, instrumental analysis such as X-ray diffraction, in the case of color materials, color density analysis, etc., and also by the indirect method described above.

In the present invention, the pKa of the organic acid obtained by protonating the anion of the anionic amphiphilic polymer of the second ink is preferably smaller than the pKa of the organic acid of the first ink, and the former pKa is preferably 4 0.5 or less, more preferably 2 or less, or 0 or less, and pKa is an acid dissociation index, and usually refers to an acid dissociation index in water. Here, the molar concentration of the acid structural unit of the polymer used is PKa is defined with respect to the polymer, the polymer aqueous solution is adjusted so that the acid structure unit is 1 mol / L, and the pH is measured directly. The hydrogen ion concentration is measured with a pH meter, and based on this, pKa = −logKa (Ka = [H ⁺ ] / [HA], A represents a conjugate base of an acid))). And as said organic acid which implement | achieves the above, a halogen-substituted benzoic acid group or a sulfonic acid group is used preferably. Moreover, it is preferable that the anion of the amphiphilic polymer of the first liquid composition is a carboxylate anion.

  In the present invention, the amphiphilic polymer of the second ink preferably has a dioxyethylene unit structure. The polyvalent cations present in the second ink coordinate with the dioxyethylene units of the amphiphilic polymer micelles. As a result, the micelles are stably dispersed in the water-based particles, and can be stably ejected when used as ink in a liquid application device such as an ink jet method.

  In the present invention, as described above, a liquid material containing a functional substance, a block polymer or a graft polymer and a liquid medium, a functional substance, and an anionic amphiphilic polymer are contained in the liquid medium. At least two types of a first liquid composition, a functional substance, and a second liquid composition containing an anionic amphiphilic polymer having a polyvalent cation as a counter cation in a liquid medium are used. . In the present invention, when two types of liquid compositions, for example, a liquid composition using a color material as a functional substance typically come into contact with a recording medium, at least one of the liquid compositions is the other. Liquid application method, image in which bleeding between two types of liquid compositions is suppressed, the fixability to a medium is improved, and the drying speed is improved by being sensitive and thickened by the liquid composition It is a forming method.

Accordingly, the two liquid compositions are different, preferably the block polymer or graft polymer is different, and is preferably sensitive to liquid contact and the block polymer or graft polymer is modified. In the present invention, in particular, the polyvalent cation used in the second liquid composition is designed to interact with the anionic portion of the amphiphilic polymer of the first liquid composition to increase the viscosity. An example of such a case will be given more specifically. There is a water-dispersed ink in which an amphiphilic block polymer includes a black pigment, and an anionic unit of the block polymer is composed of potassium carboxylate. Furthermore, as another ink composition, there is an aqueous dispersion ink in which an amphiphilic block polymer includes a yellow pigment, and the hydrophilic unit of this block polymer is composed of magnesium sulfonate or a magnesium salt of a fluoro-substituted benzoic acid. use. When the former and the latter are ink-jet-recorded at adjacent locations and are in contact with liquid, the former carboxylate anion and divalent magnesium cation interact strongly, and the pigment-encapsulated dispersion interacts more strongly and thickens. In extreme cases, the particles aggregate. In any case, the viscosity of the ink is increased, and bleed, that is, color mixing, is reduced, while drying time is shortened. The mechanism for shortening the drying time from thickening is not clear, but it is thought that the amphiphilic polymer interacts strongly with the medium in molecular kinetics during the thickening process on the medium. In this respect, it is preferable to use a dispersion in which an amphiphilic polymer, in particular, a block polymer includes a colorant, and it is preferable to use a triblock polymer. Furthermore, although the counter cation of the anionic amphiphilic polymer of the second composition of the present invention is a polyvalent cation, the counter cation is a polyvalent cation, thereby further reducing the hydrogen ion concentration of the composition. Is possible. In particular, liquid application devices, ink jet devices and the like often have insufficient hydrogen ion concentration resistance, and there are often cases where the device itself does not have an extremely acidic composition. In that sense, the composition of the present invention can be used at a neutral or near hydrogen ion concentration or weakly alkaline, which is a major feature of the present invention. The hydrogen ion concentration of the composition is preferably 3 or more, more preferably 5 or more in pH. In some cases, it may be 7 or more.
The counter cation of the anionic amphiphilic polymer of the first composition is preferably sodium, potassium, cesium or the like.

  In the present invention, as described above, when the first liquid composition and the second liquid composition are in contact with each other, at least one of these liquid compositions is thickened. The contact of the two liquid compositions means that the liquid level of the first liquid composition and the liquid level of the second liquid composition are in contact with each other. It is different from putting and mixing mechanically. For example, by ink jet recording, the liquid surfaces of two liquid compositions ejected at the same time are in contact with each other, and the carboxylate anion and divalent magnesium cation that have moved to each other from the contacted interface strongly interact with each other. The inclusion dispersion interacts more strongly and the liquid composition is thickened.

  In the present invention, a composition in which a functional substance is dispersed is preferably used. In particular, a dispersed ink composition using a color material is representative. As the colorant to be dispersed, pigments and dyes are used in a dispersed state, not in a dissolved state. Such a color material-dispersed ink composition is more effective in thickening or agglomerating in the present invention than a typical example in which a conventional color material is used in a dissolved state and an aqueous dye ink composition using a water-soluble dye. Thus, the color bleeding is greatly improved, and the effect of shortening the drying time or the short-time fixability can be greatly improved. When the forming method of the present invention is carried out using two types of ink liquid compositions, it is particularly preferable to use two types of color material-dispersed ink compositions. At that time, it is more preferable that the coloring material is included in the amphiphilic block polymer.

  Further, the liquid composition used in the above image forming process is a liquid composition in which the block polymer forms a micelle state in that the thickening is large, color mixing is largely suppressed, and the time until drying is shortened. The product is preferably used. Further, it is also preferably used in the case where a state in which a color material such as a pigment is included is formed.

  In order to obtain a composition in which the above-described functional substance, particularly a color material is included, the weight average molecular weight of the block polymer is preferably 10,000 or more, more preferably 15,000 or more. Depending on the case, it may be very preferable that it is 30,000 or more. In addition, the weight average molecular weight of the block polymer used for the purpose of greatly increasing the viscosity and largely suppressing color mixing or shortening the time until drying is similarly preferably 10,000 or more, more preferably 15,000 or more. It is. Depending on the case, it may be very preferable that it is 30,000 or more. In particular, the number average molecular weight of the hydrophobic segment of the block copolymer is 5,000 or more, more preferably 10,000 or more.

  As a preferred embodiment of the present invention, the degree of polymerization of the unit having a carboxylate anion of the amphiphilic block polymer suitably used in the first liquid composition is preferably 50 or less, and in some cases 30 or less. Or 20 or less is preferable. At this time, it is preferable to form a colorant-encapsulated state from the viewpoint that a more effective image can be formed. For this reason, the degree of polymerization of other repeating units is preferably 50 or more, more preferably 100 or more.

  In addition, the liquid composition of the present invention may contain various regulators and additives such as antioxidants, viscosity modifiers, ultraviolet absorbers, surfactants and fungicides other than those described above. . On the other hand, the action of the present invention, the thickening action which is the effect, is due to the amphiphilic block polymer or graft polymer which is a constituent factor of the present invention, and it is sufficiently effective by itself. Although it is not necessary to add another additive having a thickening action, of course, the present invention does not exclude the addition of the additive in an auxiliary sense.

  Next, an ink jet device using ink (using a color material as a functional substance) as the liquid composition according to the present invention will be described. The ink jet apparatus can be applied to various ink jet recording apparatuses such as a piezo ink jet system using a piezoelectric element and a thermal ink jet system in which heat energy is applied to perform foaming and recording.

The 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 driving circuit 60 is connected to the head 70 in addition to the X direction driving motor 56 and the Y direction driving motor 58, and the CPU 50 controls the head driving circuit 60. Drive, that is, discharge ink jet ink or the like. 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 a head (for example, an electrothermal converter or a laser beam) that generates thermal energy as energy used for ejecting ink jet ink, and ejects ink jet ink by the heat energy. Has an excellent effect. According to this method, high definition of drawing can be achieved. By using the ink of the present invention, more 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 means for the head, a pressurizing or suction means, an electrothermal converter or a heating element different from this, or a preheating means 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 for the present invention is to execute the above-described film boiling method.
In the apparatus of the present invention, the amount of ink ejected from each ejection port of the inkjet ink ejection head is preferably in the range of 0.1 picoliter to 100 picoliter.

  The ink as the liquid composition 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
<Synthesis example and used block polymer>
(1) AB block polymer composed of isobutyl vinyl ether (IBVE: A block component) and sodium 4- (2-vinyloxyethoxy) benzoate (B block component). The pKa of the acid of this polymer is 4.27.

  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 (mmol) of isobutyl vinyl ether (IBVE), 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) to confirm the completion of polymerization of component A.

  Then 10 mmol of B block component in toluene solution was added to continue the polymerization. After 16 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, then repeatedly dialyzed in a methanol solvent using a cellulose semipermeable membrane to remove the monomeric compound to obtain a diblock polymer. It was.

  The polymerization ratio of this polymer was A / B = 200/30, the number average molecule was 35000, and the weight average molecular weight was 43200. The compound was identified using NMR and GPC. 26 parts by mass of block polymer and 200 parts by mass of a sodium hydroxide aqueous solution having a pH of 13 were stirred at 0 ° C. for 3 days to obtain a sodium carboxylate polymer solution. Dialysis was performed to remove excess sodium hydroxide, drying was performed, and the solvent was distilled off to isolate a sodium carboxylate salt AB block polymer.

  (2) An AB block polymer composed of isobutyl vinyl ether (IBVE: A block component) and a sodium salt of 6- (2-vinyloxyethoxy) hexasanoic acid (B block component) was synthesized in the same manner as (1) above. Polymerization ratio A / B = 200/28, number average molecular weight 36000, weight average molecular weight 45000 (all before hydrolysis), pKa of the acid of this polymer is 4.92.

  (3) A diblock polymer comprising isobutyl vinyl ether, 2-vinyloxy-1-biphenyloxyethyl (A block component), and sodium 5- (2-vinyloxyethoxy) benzene-1,3-dicarboxylate (B block component). Synthesized in the same manner as in (1) above. Polymerization ratio A / B / C = 100/15, number average molecular weight 15000, weight average molecular weight 18200 (all before hydrolysis), pKa of the acid of this polymer is 4.19.

  (4) From isobutyl vinyl ether, 2-vinyloxy-1-biphenyloxyethyl (A block component) and magnesium 4- (2-vinyloxyethoxy) -2,3,5,6-tetrafluorobenzoate (B block component) A diblock polymer was synthesized as described above. Polymerization ratio A / B = 100/17, number average molecular weight 16000, weight average molecular weight 19900 (all before hydrolysis), pKa of the acid of this polymer is 1.97.

  (5) A diblock polymer comprising isobutyl vinyl ether, 2-vinyloxy-1-biphenyloxyethyl (A block component) and 4- (2-vinyloxyethoxy) -magnesium benzenesulfonate (B block component) is the above (1). Was synthesized in the same manner as above. The polymerization ratio A / B = 100/15, the number average molecular weight 14800, the weight average molecular weight 18500 (all before hydrolysis), and the pKa of the acid of this polymer was −0.81.

  (6) From isobutyl vinyl ether, 2-vinyloxy-1-biphenyloxyethyl (A block component), 2-methoxyethyl vinyl ether (B block component), and sodium 4- (2-vinyloxyethoxy) benzoate (C block component) The resulting triblock polymer was synthesized as described above. Polymerization ratio A / B / C = 100/116/9, number average molecular weight 25300, weight average molecular weight 30800 (both before hydrolysis), pKa of the acid of this polymer is 4.34.

  (7) The block copolymer (7) was synthesized in the same manner using 2-ethoxyethyl vinyl ether instead of IBVE as the component A of the block copolymer (1) of Synthesis Example 1. The pKa of the acid of this polymer is 4.94. It was -21 degreeC when Tg of this polymer was measured by DSC (DSC7 by Perkin-Elmer Co.).

  (8) An AB block polymer comprising 2- (4-methylbenzeneoxy) ethyl vinyl ether (TolOVE: A block component) and sodium 4- (2-vinyloxyethoxy) benzoate (B block component) is combined with the above (1). It synthesized similarly. The polymerization ratio A / B = 100/15, the number average molecular weight 17000, the weight average molecular weight 19000 (both before hydrolysis), and the pKa of the acid of this polymer was 4.30.

  (9) Isobutyl vinyl ether, 2-vinyloxy-1-biphenyloxyethyl (A block component), 2-methoxyethyl vinyl ether (B block component) and 4- (2-vinyloxyethoxy) -sodium benzenesulfonate (C block component) ) Was synthesized in the same manner as described above. Polymerization ratio A / B / C = 100/80/15, number average molecular weight 26000, weight average molecular weight 33000 (both before hydrolysis), and pKa of the acid of this polymer was −0.81.

  (10) From isobutyl vinyl ether, 2-vinyloxy-1-biphenyloxyethyl (A block component), diethylene glycol methyl vinyl ether (B block component) and 4- (2-vinyloxyethoxy) -sodium benzenesulfonate (C block component) The resulting triblock polymer was synthesized as described above. Polymerization ratio A / B / C = 100/80/15, number average molecular weight 29500, weight average molecular weight 37400 (both before hydrolysis), and pKa of the acid of this polymer was −0.81.

Example 1
3 parts by mass of magenta pigment (CI PigmentRed122), 5 parts by mass of the block copolymer of (1), and 15 parts by mass of diethylene glycol were added to 178 parts by mass of ion-exchanged water, and dispersed using an ultrasonic homogenizer. The mixture was pressure filtered through a 1 μm filter to prepare a pigment-dispersed aqueous ink. The dispersibility of the pigment was good.

  3 parts by mass of a black pigment (trade name Mogul L, manufactured by Cabot Corporation), 5 parts by mass of the block copolymer of (5), and 15 parts by mass of diethylene glycol were added to 178 parts by mass of ion-exchanged water and dispersed using an ultrasonic homogenizer. The mixture was filtered under pressure through a 1 μm filter to prepare a pigment-dispersed aqueous ink, and the pH was adjusted to 6.2. The dispersibility of the pigment was good.

  As described above, ink jet recording was performed using two kinds of inks. An ink tank of an ink jet printer (trade name BJF800, Bubble Jet (registered trademark) manufactured by Canon Inc.) is filled with two ink compositions, and alternating black and magenta patterns are recorded on plain paper at 1 mm intervals. There was almost no blurring of the black and magenta border. When observed with a microscope, the average width of bleeding was 0.10 mm.

  Further, when the two types of ink were mixed in a vial of 0.3 ml, the viscosity was clearly increased. The former ink was 4.8 cps and the latter was 4.9 cps, but after mixing it was 31.4 cps (viscosity was measured with DAR100 manufactured by Rheologica).

Comparative Example 1
3 parts by weight of black pigment (trade name Mogul L, manufactured by Cabot), 3 parts by weight of sodium styrene acrylate (molecular weight 6,300, polymerization ratio 1: 1) and 15 parts by weight of diethylene glycol were added to 178 parts by weight of ion-exchanged water, After dispersion using an ultrasonic homogenizer, the mixture was filtered under pressure through a 1 μm filter to prepare a black pigment dispersed aqueous ink. Using this and a magenta ink provided with an ink jet printer (trade name BJF800), a print test similar to that in Example 1 was performed, and a clear blur was visually observed at the boundary between black and magenta. When observed with a microscope, the average width of bleeding was 0.24 mm.

Example 2
26 parts by mass of the block copolymer (2) used in Example 1 and 10 parts by mass of a fat-soluble dye oil blue N (trade name, manufactured by Aldrich) were co-dissolved in 85 parts by mass of dimethylformamide, and 400 parts by mass of distilled water. Was used to convert to an aqueous phase to obtain an ink. Similarly, a yellow ink having a pH of 5.9 was prepared using the block polymer (5) and a yellow fat-soluble dye (VALIFISTERYLOW 3108, manufactured by Orient Chemical Co., Ltd.). When alternating patterns were recorded on plain paper at 1 mm intervals, there was almost no blurring of the boundary lines. When observed with a microscope, the average width of bleeding was 0.11 mm.
Immediately after printing, 10 ml of distilled water was used to wet about an area of about 50 cm ² , but no color bleeding occurred.

Example 3
26 parts by mass of block copolymer (7) and 10 parts by mass of fat-soluble dye oil blue N (trade name, manufactured by Aldrich) are co-dissolved in dimethylformamide and converted into an aqueous phase using 400 parts by mass of distilled water. A blue ink was obtained. Similarly, a yellow ink having a pH of 4.1 was prepared using the block polymer (4) and a yellow fat-soluble dye (VALIFISTERYLOW 3108, manufactured by Orient Chemical Co., Ltd.). As in Example 1, when alternating patterns were recorded on plain paper at 1 mm intervals, there was almost no blurring of the boundary lines. When observed with a microscope, the average width of bleeding was 0.12 mm.

Immediately after printing, 10 ml of distilled water was used to wet about an area of about 50 cm ² , but no color bleeding occurred.
The 2-ethoxyethyl vinyl ether polymer that is the component A of the block copolymer (7) changes from hydrophobic to hydrophilic at 20 ° C. or lower. That is, when it is 20 ° C. or higher, it becomes amphiphilic and forms micelles, but when it becomes 20 ° C. or lower, the micelles collapse. When the ink composition was cooled to 0 ° C. to collapse the micelles, the color material was eluted and floated on the upper part of the ink, and the aqueous phase was completely decolorized. From this, it was found that the coloring material was completely encapsulated in the block copolymer micelle. The density ratio of the ink composition and the decolored water phase based on the intensity ratio at λmax was 0.5% or less of the former. It was found that 99% or more of the coloring material was included.

Example 4
15 parts by mass of block polymer (3) and 7 parts by mass of black pigment (trade name Mogul L, manufactured by Cabot Corporation) are mixed with 150 parts by mass of dimethylformamide, and converted to an aqueous phase using 500 parts by mass of distilled water to produce black. An ink composition was obtained.

  15 parts by mass of block polymer (4), C.I. I. 7 parts by weight of CI Pigment Blue-15: 3 are co-dissolved in 250 parts by weight of THF and 80 parts by weight of ethylene glycol, converted to an aqueous phase using 500 parts by weight of distilled water, THF is distilled off under reduced pressure, pH 7.5 A blue ink composition was obtained.

  As in Example 1, when alternating patterns were recorded on plain paper at 1 mm intervals, there was almost no blurring of the boundary lines. When observed with a microscope, the average width of bleeding was 0.12 mm.

Immediately after printing, 10 ml of distilled water was used to wet about an area of about 50 cm ² , but no color bleeding occurred.
Each of the above liquid compositions was frozen with an TEM (manufactured by FEI, Cryotransfer), and observed with an electron microscope. As a result, only spherical micelle particles were observed, and the colorant was completely encapsulated in the block polymer. I understood it.

Example 5
15 parts by mass of block polymer (3) and 7 parts by mass of yellow fat-soluble dye (Orient Chemical Co., Ltd., VALIFASTYELLOW3108) are mixed with 150 parts by mass of dimethylformamide, and converted to an aqueous phase using 500 parts by mass of distilled water, An ink composition was obtained.

  15 parts by mass of block polymer (5), C.I. I. 7 parts by weight of CI Pigment Blue-15: 3 are co-dissolved in 250 parts by weight of THF and 80 parts by weight of ethylene glycol, and converted to an aqueous phase using 500 parts by weight of distilled water, and THF is distilled off under reduced pressure. A blue ink composition was obtained.

  As in Example 1, when alternating patterns were recorded on plain paper at intervals of 1 mm, there was almost no blurring of the borderline between blue and yellow. When observed with a microscope, the average width of bleeding was 0.11 mm.

Immediately after printing, 10 ml of distilled water was used to wet about an area of about 50 cm ² , but no color bleeding occurred.
When each of the above liquid compositions was frozen with an electron microscope using a TEM (FEI, Cryotransfer) and observed with an electron microscope, only spherical micelle particles were observed, and the colorant was completely encapsulated in the block polymer. I understood.

Comparative Example 2
A dye ink composition was obtained from 1.5 parts by mass of sodium azulene sulfonate, which is a blue water-soluble dye, 10 parts by mass of ethylene glycol, 10 parts by mass of diethylene glycol, and 78.5 parts by mass of distilled water, and the pH was 5.1. Adjusted.

  26 parts by mass of block copolymer (6) and 10 parts by mass of yellow fat-soluble dye (Orient Chemical Co., Ltd., VALIFASTYELLOW3108) are co-dissolved in 80 parts by mass of dimethylformamide, and converted to an aqueous phase using 400 parts by mass of distilled water. A yellow ink was obtained.

When alternating patterns were recorded on plain paper at intervals of 1 mm as in Example 1, the blurring of the boundary line was visually observed, and the average width of the blurring was 0.21 mm when observed with a microscope.
Further, immediately after printing, when 10 ml of distilled water was applied over an area of about 50 cm ² , color bleeding and mixing occurred at the same time and the recording pattern changed greatly.

Comparative Example 3
3 parts by mass of magenta pigment (CI PigmentRed122), 5 parts by mass of sodium styrene acrylate block polymer (1: 1 copolymer, number average molecular weight 6,300, weight average molecular weight 9,200), and 15 parts by mass of diethylene glycol In addition to 178 parts by mass of ion-exchanged water, the mixture was dispersed using an ultrasonic homogenizer. The mixture was pressure filtered through a 1 μm filter to prepare a pigment-dispersed aqueous ink. The dispersibility of the pigment was good.

  Black pigment (trade name Mogul L, manufactured by Cabot Corporation) 3 parts by mass, random copolymer of sodium styrenecarboxylate and styrene (1: 2 copolymer, number average molecular weight 4,500, weight average molecular weight 7,900) 5 Part by mass and 15 parts by mass of diethylene glycol were added to 178 parts by mass of ion-exchanged water and dispersed using an ultrasonic homogenizer. The mixture was pressure filtered through a 1 μm filter to prepare a pigment-dispersed aqueous ink. The dispersibility of the pigment was good.

When alternating patterns were recorded on plain paper at intervals of 1 mm as in Example 1, the blurring of the boundary line was visually observed, and the average width of the blurring was 0.21 mm when observed with a microscope.
Further, immediately after printing, when 10 ml of distilled water was applied over an area of about 50 cm ² , color bleeding and mixing occurred simultaneously, and the recording pattern changed greatly.

Example 6
Sodium styrene acrylate block polymer (1: 1 copolymer, number average molecular weight 6,300, weight average molecular weight 9,200) 7 parts by mass, black pigment (trade name Mogul L, manufactured by Cabot Corp.) 7 parts by mass, ethylene 40 parts by mass of glycol and 200 parts by mass of distilled water were dispersed using an ultrasonic homogenizer. The mixture was filtered under pressure through a 1 μm filter, and the pH was adjusted to 9.3 to obtain a pigment-dispersed aqueous ink.

  From 1.5 parts by mass of sodium azulene sulfonate, which is a blue water-soluble dye, 10 parts by mass of ethylene glycol, 10 parts by mass of diethylene glycol, 3 parts by mass of block polymer (5), and 77.5 parts by mass of distilled water, pH 4. 8 dye ink compositions were obtained.

When alternating patterns were recorded on plain paper at intervals of 1 mm as in Example 1, the blur of the boundary line was observed with a microscope, and the average width of the blur was 0.20 mm.
Immediately after printing, 10 ml of distilled water was applied over an area of about 50 cm ² , and only slight color bleeding and mixing occurred.
When the aqueous solution of the pigment-dispersed ink composition was frozen with TEM (manufactured by FEI, Cryotransfer) and observed with an electron microscope, 60% of the pigment particles were exposed.

Example 7
15 parts by mass of block polymer (3) and 7 parts by mass of black pigment (trade name Mogul L, manufactured by Cabot) are mixed with 150 parts by mass of dimethylformamide, and 500 parts by mass of distilled water and the carboxylic acid part of the block polymer are mixed. One equivalent of KOH was added to obtain a black ink composition.

  From 1.5 parts by mass of sodium azulene sulfonate, which is a blue water-soluble dye, 10 parts by mass of ethylene glycol, 10 parts by mass of diethylene glycol, 3 parts by mass of block polymer (4), and 77.5 parts by mass of distilled water, pH 5. 1 dye ink composition was obtained.

When alternating patterns were recorded on plain paper at intervals of 1 mm as in Example 1, the blur of the boundary line was observed with a microscope, and the average width of the blur was 0.12 mm.
Further, when the sample was wetted with 10 ml of distilled water immediately after printing over an area of about 50 cm ^2, no color bleeding or mixing was observed.

  When the aqueous pigment solution was frozen with a TEM (manufactured by FEI, Cryotransfer) and observed with an electron microscope, only the spherical particles were observed, and it was found that the colorant was completely encapsulated in the block polymer. It was.

Example 8
3 parts by mass of magenta pigment (CI PigmentRed122), 5 parts by mass of the block copolymer of (8) and 15 parts by mass of diethylene glycol were added to 178 parts by mass of ion-exchanged water, and dispersed using an ultrasonic homogenizer. The mixture was pressure filtered through a 1 μm filter to prepare a pigment-dispersed aqueous ink. The dispersibility of the pigment was good.

  3 parts by weight of black pigment (trade name Mogul L, manufactured by Cabot), 5 parts by weight of the block copolymer of (9), 15 parts by weight of diethylene glycol and 5 parts by weight of magnesium nitrate are added to 173 parts by weight of ion-exchanged water, and an ultrasonic homogenizer Was used to disperse. The mixture was filtered under pressure through a 1 μm filter to prepare a pigment-dispersed aqueous ink, and the pH was adjusted to 6.2. The dispersibility of the pigment was good.

  As described above, ink jet recording was performed using two kinds of inks. An ink tank of an ink jet printer (trade name BJF800, Bubble Jet (registered trademark) manufactured by Canon Inc.) is filled with two ink compositions, and alternating black and magenta patterns are recorded on plain paper at 1 mm intervals. There was almost no blurring of the black and magenta border. When observed with a microscope, the average width of bleeding was 0.10 mm.

  Further, when the two types of ink were mixed in a vial of 0.3 ml, the viscosity was clearly increased. The former ink was 4.2 cps and the latter was 5.0 cps, but after mixing it was 32.0 cps (viscosity was measured with DAR100 manufactured by Rheologica).

Example 9
3 parts by mass of magenta pigment (CI PigmentRed122), 5 parts by mass of the block copolymer of (8) and 15 parts by mass of diethylene glycol were added to 178 parts by mass of ion-exchanged water, and dispersed using an ultrasonic homogenizer. The mixture was pressure filtered through a 1 μm filter to prepare a pigment-dispersed aqueous ink. The dispersibility of the pigment was good.

  3 parts by weight of a black pigment (trade name Mogul L, manufactured by Cabot), 5 parts by weight of the block copolymer of (10), 15 parts by weight of diethylene glycol and 5 parts by weight of magnesium nitrate are added to 173 parts by weight of ion-exchanged water, and an ultrasonic homogenizer Was used to disperse. The mixture was filtered under pressure through a 1 μm filter to prepare a pigment-dispersed aqueous ink, and the pH was adjusted to 6.2. The dispersibility of the pigment was good.

  As described above, ink jet recording was performed using two kinds of inks. An ink tank of an ink jet printer (trade name BJF800, Bubble Jet (registered trademark) manufactured by Canon Inc.) is filled with two ink compositions, and alternating black and magenta patterns are recorded on plain paper at 1 mm intervals. There was almost no blurring of the black and magenta border. When observed with a microscope, the average width of bleeding was 0.10 mm.

  Further, when the two types of ink were mixed in a vial of 0.3 ml, the viscosity was clearly increased. The former ink was 4.2 cps and the latter was 5.2 cps, but after mixing it was 32.4 cps (viscosity was measured with DAR100 manufactured by Rheologica).

Example 10
Second ink composition using block polymer (4), block polymer (5), block polymer (9) and block polymer (10) obtained in Example 3, Example 5, Example 8, and Example 9 Each product 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.
Δ: The ratio of blurring and chipping to the entire square image of 50 mm × 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.

  Second ink composition using block polymer (4), block polymer (5), block polymer (9) and block polymer (10) obtained in Example 3, Example 5, Example 8, and Example 9 When the product was evaluated, the evaluation results were, in order, ○, ○, ◎, and ◎.

  The present invention uses a liquid composition containing two or more kinds of characteristics containing functional substances such as a color material, and when the liquid composition is brought into contact with the liquid composition, the liquid composition is thickened. The recording method is capable of forming or patterning. It is possible to suppress inconvenient mixing of functional materials such as color materials on the medium, and it is possible to obtain good fixability of color materials and the like in the recording portion and to form a good pattern, so that ink jet recording is possible. It can be used in the field of digital printing technology such as methods.

It is a block diagram which shows the structure of an inkjet recording device.

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 (13)

  An image forming method for forming an image on a recording medium by applying two or more liquid compositions onto the recording medium, comprising a functional substance, an anionic amphiphilic polymer, and a liquid medium At least a first liquid composition, a functional substance, a polyvalent cation, an anionic amphiphilic polymer, and a liquid medium, and the first liquid Preparing a plurality of liquid compositions in which at least one of the polymer of the composition and the second liquid composition is a block polymer or a graft polymer, and the first liquid composition and the second liquid composition Applying to the recording medium, bringing the first liquid composition and the second liquid composition into contact with each other, and causing at least one of these liquid compositions to thicken. An image forming method.   The image forming method according to claim 1, wherein the polyvalent cation of the second liquid composition is a metal cation.   The image forming method according to claim 1, wherein the polymers in the first and second liquid compositions are both block polymers.   The image forming method according to claim 1, wherein the functional substance is encapsulated by the amphiphilic polymer.   5. The pKa of the organic acid formed by protonating the anion of the anionic amphiphilic polymer of the second liquid composition is 2 or less, The image forming method according to item.   The image forming method according to claim 5, wherein the organic acid is a halogen-substituted benzoic acid group or a sulfonic acid group.   The image forming method according to claim 1, wherein the anionic amphiphilic polymer of the second liquid composition contains a dioxyethylene unit structure.   The image forming method according to claim 1, wherein an anion of the amphiphilic polymer of the first liquid composition is a carboxylate anion.   The image forming method according to claim 1, wherein the amphiphilic polymer has a repeating structure of monomer units composed of alkenyl ethers.   The image forming method according to claim 1, wherein the functional substance is a color material.   A method of applying a liquid composition containing a functional substance to a pattern forming medium to form a pattern comprising an adhesion region of the functional substance, the functional substance, an anionic amphiphilic polymer, a liquid A first liquid composition containing a medium, a functional substance, a polyvalent cation, an anionic amphiphilic polymer, and a second liquid composition containing a liquid medium, Preparing a plurality of liquid compositions in which at least one of the polymer of one liquid composition and the second liquid composition is a block polymer or a graft polymer; and the first liquid composition and the second liquid composition Providing a product on the pattern forming medium, bringing the first liquid composition and the second liquid composition into contact with each other, and causing at least one of these liquid compositions to thicken. Characterized by having That pattern forming method.   The pattern formation method according to claim 11, wherein the liquid composition is applied by an ink jet method.   A first liquid composition containing a functional substance, an anionic amphiphilic polymer, and a liquid medium, a functional substance, a polyvalent cation, an anionic amphiphilic polymer, and a liquid medium And at least one of the first liquid composition and the polymer of the second liquid composition is composed of a block polymer or a graft polymer, and the first liquid composition And the second liquid composition come into contact with each other to cause energy to act on a plurality of liquid compositions in which at least one of these liquid compositions is thickened, and thereby the plurality of liquid compositions are recorded on the recording medium A liquid application apparatus comprising: a liquid application unit for applying the liquid application unit; and a driving unit for driving the liquid application unit.

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