JP2005344105A - Polymer, polymer-containing composition containing the same, ink composition, and ink applying method, image forming method and image forming apparatus which make use of ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer capable of dispersing a functional material in a solvent well. <P>SOLUTION: The polymer has a specific repeating structural unit represented by general formula (1) and having in the side chain at least one selected from a sulfonic acid, a sulfonic acid ester and a sulfonic acid salt, and a specific repeating structural unit represented by general formula (2) and having in the side chain at least one selected from a carboxylic acid, a carboxylic acid ester and a carboxylic acid salt as a copolymerized composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel polymer compound useful as various functional materials, a polymer-containing composition containing the same, an ink composition, and an ink application method and apparatus using the ink composition. Particularly preferably, the present invention relates to a recording material such as an ink composition using such a compound together with a solvent or a dispersion medium and a color material, and an ink application method and apparatus using the composition.

  In aqueous dispersion materials containing functional substances, conventionally, as functional materials, herbicides, pesticides such as insecticides, anticancer agents, antiallergic agents, medicines such as anti-inflammatory agents, and inks having colorants, Color materials such as 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 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.

  Ink used in these methods usually uses an aqueous dye solution, so that bleeding occurs when colors are superimposed, or a phenomenon called feathering appears in the fiber direction of the paper at the recording location on the recording medium. was there. In order to improve these, the use of pigment-dispersed ink has been studied (see Patent Document 1). As an example of a pigment dispersion method, an example using a polymer having a sulfonic acid group (see Patent Document 2) has been reported. However, many improvements are still desired.

  In the production of an ink composition or a toner composition, a number of methods for dispersing a coloring material in a solution in which a binder resin is dissolved have been conventionally performed. As a binder resin generally used for wet dispersion of pigments, for example, styryl, acrylic, and methacrylic polymer compounds are used. In preparing a pigment ink based on a solvent, particularly water, it is preferable to use a polymer material having an ionic functional group.

On the other hand, a polymer compound having a polyalkenyl ether main chain is also known as a polymer material having a flexible polymer chain, but it is almost impossible to introduce an ionic functional group into a repeating unit of the polymer compound. Not done. Slightly, some carboxylic acids and their esters are disclosed as possible (see Non-Patent Document 1), but the present situation is that a more stable polymer compound is required.
US Pat. No. 5,085,698 US Pat. No. 5,713,993 “Journal of Polymer Science Part A Polymer Chemistry” Vol. 27, p. 3303-3314, 1989

  The present invention is intended to provide a polymer compound that can satisfactorily disperse a functional substance in a solvent.

  In addition, the present invention intends to provide a polymer-containing composition and an ink composition having good dispersibility containing the polymer compound.

  The present invention also provides a liquid application method, apparatus, image forming method, and image forming medium using the composition.

  The polymer compound provided by the present invention contains a repeating unit structure represented by the following general formula (1) and a repeating unit structure represented by the following general formula (2) as a copolymer composition. It is a characteristic high molecular compound.

  General formula (1)

（式中、Ａは置換されていても良いポリアルケニル基を表す。Ｂは−Ｏ−、―ＯＣＯ―、―ＣＯＯ―、―ＣＯＮＲ^１―、―ＣＨ_２―から選ばれる構造のうちのいずれかを表す。Ｒ^１は水素原子、または炭素原子数１から３までの直鎖状または分岐状の置換されていても良いアルキル基を表す。Ｄは炭素原子数１から１５までの直鎖状または分岐状の置換されていても良いアルキレン基を表し、前記アルキレン基内のメチレン基は酸素原子または芳香族環に置換されてもよい。また、ｍは０から３０までの整数を表し、ｍが複数の場合、それぞれのＤは異なっていても良い。Ｅは置換されていても良い芳香族環を表す。また、ｎは０から１０までの整数を表し、ｎが複数の場合、それぞれのＥは異なっていても良い。また、ｍ＋ｎ≧１である。Ｒは−ＳＯ_３Ｈ、−ＳＯ_３Ｒ^２、−ＳＯ_３−Ｍを表す。Ｒ^２は炭素原子数１から５までの直鎖状、または分岐状の置換されていても良いアルキル基、または置換されていても良い芳香族環を表す。Ｍは１価または多価のカチオンを表す。）
一般式（２）

(In the formula, A represents an optionally substituted polyalkenyl group. B represents any one of structures selected from —O—, —OCO—, —COO—, —CONR ¹ —, —CH ₂ —. R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, which may be substituted, and D is a straight chain having 1 to 15 carbon atoms or A branched alkylene group which may be substituted, a methylene group in the alkylene group may be substituted with an oxygen atom or an aromatic ring, and m represents an integer of 0 to 30; In a plurality of cases, each D may be different, E represents an optionally substituted aromatic ring, n represents an integer from 0 to 10, and when n is a plurality, each E May be different, and m + n ≧ 1. .R is ^{_{-SO 3 H, -SO 3 R 2}} , represents a _-SO 3 -M .R ² is a linear or branched optionally substituted alkyl group having 1 to 5 carbon atoms, Or an aromatic ring which may be substituted; M represents a monovalent or polyvalent cation.)
General formula (2)

（式中、Ａは置換されていても良いポリアルケニル基を表す。Ｂ’は−Ｏ−、―ＯＣＯ―、―ＣＯＯ―、―ＣＯＮＲ^１―、から選ばれる構造のうちのいずれかを表す。Ｒ^１は水素原子、または炭素原子数１から３までの直鎖状または分岐状の置換されていても良いアルキル基を表す。Ｄは炭素原子数１から１５までの直鎖状または分岐状の置換されていても良いアルキレン基を表し、前記アルキレン基内のメチレン基は酸素原子または芳香族環に置換されてもよい。また、ｍは０から３０までの整数を表し、ｍが複数の場合、それぞれのＤは異なっていても良い。Ｅ’は置換されていても良いアルキル基または芳香族環を表す。また、ｎ’は１から１０までの整数を表し、ｎ’が複数の場合、それぞれのＥ’は異なっていても良い。Ｒ’は−ＣＯＯＨ、−ＣＯＯＲ^２、−ＣＯＯ−Ｍを表す。Ｒ^２は炭素原子数１から５までの直鎖状、または分岐状の置換されていても良いアルキル基または芳香族環を表す。Ｍは１価または多価のカチオンを表す。また、ｌは１または複数である。）

(In the formula, A represents an optionally substituted polyalkenyl group. B ′ represents any one of structures selected from —O—, —OCO—, —COO—, —CONR ¹ —). R ¹ represents a hydrogen atom, or a linear or branched alkyl group having 1 to 3 carbon atoms, and D represents a linear or branched alkyl group having 1 to 15 carbon atoms. An alkylene group which may be substituted, a methylene group in the alkylene group may be substituted with an oxygen atom or an aromatic ring, and m represents an integer from 0 to 30; , Each D may be different, E ′ represents an optionally substituted alkyl group or an aromatic ring, n ′ represents an integer of 1 to 10, and when n ′ is plural, Each E ′ may be different and R ′ is —COO. , -COOR ^2, represents a -COO-M .R ² is .M monovalent representing a linear or branched optionally substituted alkyl group or an aromatic ring having 1 to 5 carbon atoms Or represents a polyvalent cation, and 1 is one or more.)

  The present invention also includes a polymer-containing composition comprising the polymer compound of the present invention, a solvent or dispersion medium, and a functional substance.

  The invention also includes an ink composition wherein the functional substance is a color material.

  The present invention also includes an ink application method comprising the step of applying the ink composition of the present invention to a medium. In the ink application method of the present invention, a substance or composition that changes the pH of the ink composition may be provided in advance on the medium.

  Furthermore, the present invention is a medium for forming an image by applying an ink composition, comprising a substance or a composition that changes the pH of the ink composition by contact with the ink composition. Includes the image forming media characterized.

  In addition, the present invention includes an ink application unit for applying energy to the ink composition of the present invention to apply ink to the medium, and a drive unit for driving the ink application unit. Including an ink applicator.

  According to the present invention, a novel polymer compound and a block polymer compound that can satisfactorily disperse a functional substance in a solvent can be provided.

  Moreover, this invention can provide the polymer containing composition and ink composition which have favorable dispersibility using the said block polymer compound.

  In addition, according to the present invention, it is possible to provide an image forming method and an image forming apparatus using the above composition having good dispersibility.

  In the present invention, the aromatic ring indicates a structure having a cyclic π electron cloud delocalized above and below the molecular plane, such as benzene.

  In addition, the side chain has a sulfonic acid represented by the general formula (1), or a sulfonic acid ester such as methyl sulfonate, ethyl sulfonate, or propyl sulfonate, or sodium sulfonate, potassium sulfonate, or sulfonic acid. A repeating unit structure having a sulfonic acid derivative such as sulfonates such as ammonium and the carboxylic acid represented by the general formula (2), or carboxylic acid esters such as methyl carboxylate, ethyl carboxylate, and benzyl carboxylate, Alternatively, the polymer compound is characterized by being a polymer compound copolymerized with a repeating unit structure having a carboxylic acid derivative such as a carboxylate such as sodium carboxylate, potassium carboxylate, or ammonium carboxylate.

  Since sulfonic acid or sulfonate is highly acidic as an acid, protons of sulfonic acid or cations of sulfonate are easily liberated in an aqueous solution, and ions are dissociated even in a low pH region. Disperse more stably. Further, since the polymer compound has a plurality of sulfonic acid groups which are ionic functional groups having a high degree of dissociation, it is extremely useful in that it can be provided as a functional polymer material. In addition, sulfonic acid and sulfonate are often obtained by hydrolyzing sulfonic acid ester. Therefore, sulfonic acid ester structure is very useful as a synthesis precursor of sulfonic acid and sulfonate, Even in the form of sulfonate, it is very useful as a highly polar compound.

  In the repeating unit structure represented by the general formula (2), a carboxylic acid group is bonded from the main chain through 2 or more atoms, and is not directly connected to the main chain, but through some linking group, In addition, a carboxylic acid, a carboxylic acid ester, or a carboxylate salt is present through a linking group having 2 or more atoms. This is because, for example, carboxylic acid or carboxylic acid ester or carboxylate salt is present by binding to the main chain in a manner in which mobility is restricted, such as a polymer polymer of acrylic acid, methacrylic acid, itaconic acid or derivatives thereof. Instead, the carboxylic acid or carboxylic acid ester or carboxylic acid salt is in a state where it can freely undergo molecular motion through a linking group such as an alkylene group or an alkyleneoxy group. The number of atoms of the linking group is 2 or more, preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more.

  In a structure that is directly connected to the main chain too much, the mobility of carboxylic acid or carboxylic acid ester or carboxylic acid base may be limited, and the interaction between molecules and within the molecule may not be sufficiently exerted. Therefore, a free carboxylic acid structure and a carboxylate structure are preferred as those in which these interactions work. However, these free carboxylic acid structures and carboxylates are often obtained by hydrolysis of carboxylic acid esters. For this reason, the carboxylic acid ester structure is very useful as a precursor for the synthesis of a free carboxylic acid structure and a carboxylate, even though it does not allow much interaction within and between molecules.

  Therefore, the polymer compound obtained by copolymerizing the repeating unit structures represented by the general formulas (1) and (2) of the present invention has both the above functions, and further has a sulfonic acid group and a carboxylic acid group having different pKa. Can be provided as a functional polymer material that can control the structure of the polymer compound and the degree of dissociation of protons or cations of these ionic functional groups depending on pH. But it is extremely useful.

  In the present invention, the content ratio of the repeating unit structure represented by the general formula (1) and the repeating unit structure represented by the general formula (2) contained in the polymer compound is 1:99 to 99: 1. The range is preferably 10:90 to 90:10, more preferably 30:70 to 70:30.

  Moreover, in this invention, the copolymer composition of the repeating unit structure represented by General formula (1) and the repeating unit structure represented by General formula (2) contained in a high molecular compound is General formula (1). ) And (2) may be a random copolymer in which the repeating unit structures are randomly arranged, or may be an alternating copolymer in which the repeating unit structures of the general formulas (1) and (2) are alternately arranged. ) And (2) may be a gradient copolymer in which the composition ratio of the repeating unit structure gradually changes.

  The present invention also provides a polymer compound obtained by copolymerizing at least one repeating unit structure represented by the general formulas (1) and (2), each represented by the general formulas (1) and (2). A plurality of repeating unit structures may be included, and other repeating unit structures other than the general formulas (1) and (2) may be included.

  As a specific example of the repeating unit structure represented by the general formula (1),

等の、一般式（１）においてｎ＝０のときに得られる、スルホン酸基が脂肪族炭素と結合した脂肪族スルホン酸誘導体が挙げられるが、これらに限定されない。

An aliphatic sulfonic acid derivative in which a sulfonic acid group is bonded to an aliphatic carbon, which is obtained when n = 0 in the general formula (1), is not limited thereto.

  Further, a preferred embodiment of the present invention includes a repeating unit structure having an aromatic sulfonic acid derivative having a sulfonic acid group bonded to an aromatic carbon in the side chain, wherein n ≧ 1 in the general formula (1). When the sulfonic acid group which is an electron withdrawing group has a high acidity due to its attraction action and the carbon atom (α-carbon) to which the sulfonic acid group is bonded, and the α-carbon has a hydrogen atom (α-hydrogen), Hydrogen atoms are easily desorbed. Therefore, an aromatic sulfonic acid having no α-hydrogen is more preferably used. As a specific example of the above repeating unit structure,

が挙げられるが、これらに限定されない。
（Ｐｈは、１，４−フェニレンまたは１，３−フェニレンを表す。Ｐｙｒは２，５−ピリジルを表す。Ｎｐは、２，６−ナフチルまたは１，４−ナフチルまたは１，５−ナフチルを表す。）
一般式（２）で表される繰り返し単位構造の具体例として、

However, it is not limited to these.
(Ph represents 1,4-phenylene or 1,3-phenylene. Pyr represents 2,5-pyridyl. Np represents 2,6-naphthyl, 1,4-naphthyl, or 1,5-naphthyl. .)
As a specific example of the repeating unit structure represented by the general formula (2),

等の一般式（２）においてｌ＝１である、モノカルボン酸構造が挙げられるがこれらに限定されない。
（Ｐｈは、１，４−フェニレンまたは１，３−フェニレンを表す。Ｐｙｒは２，５−ピリジルを表す。Ｎｐは、２，６−ナフチルまたは１，４−ナフチルまたは１，５−ナフチルを表す。）
以下にｌが複数の時の具体例を示すがこれらに限定されない。

Examples include, but are not limited to, monocarboxylic acid structures in which l = 1 in general formula (2).
(Ph represents 1,4-phenylene or 1,3-phenylene. Pyr represents 2,5-pyridyl. Np represents 2,6-naphthyl, 1,4-naphthyl, or 1,5-naphthyl. .)
Specific examples of when l is plural are shown below, but are not limited thereto.

（Ｐｈは、１，３，５−フェニレンを表す。Ｎｐは、１，２，３−ナフチル、１，２，４−ナフチル、１，５，６−ナフチル、１，５，７−ナフチル、２，５，６−ナフチル、または２，５，７−ナフチルを表す。）

(Ph represents 1,3,5-phenylene. Np represents 1,2,3-naphthyl, 1,2,4-naphthyl, 1,5,6-naphthyl, 1,5,7-naphthyl, 2 , 5,6-naphthyl or 2,5,7-naphthyl.)

  Further, the present invention is a block polymer having at least two or more block segments, wherein at least one block segment of the block polymer is a sulfonic acid or sulfonic acid in a side chain represented by the general formula (1). A repeating unit structure having at least one selected from esters and sulfonates, and a repeating unit having at least one selected from carboxylic acids, carboxylic esters and carboxylates in the side chain represented by the general formula (2) It is a block polymer compound characterized by containing a copolymer composition with a unit structure. The block polymer described in the present invention refers to a copolymer in which different types of block segment structures are linked on a polymer chain, and also refers to a block copolymer or block copolymer. A block polymer compound that is amphiphilic is preferable.

  The amphiphilic block polymer compound is a polymer compound having at least one or more amphiphilic and lyophobic block segments. The above-mentioned amphiphilic property represents a property of having a large affinity for a main solvent used in a polymer-containing composition described later, and the lyophobic property is a property of a low affinity for a solvent. . When the solvent is water, the polymer compound of the present invention preferably has at least one or more hydrophilic and hydrophobic block segments.

  In the block polymer compound of the present invention, at least one block segment is hydrophobic, and at least one block segment is hydrophilic, so that amphiphilicity is expressed. The hydrophilicity is a property that has a high affinity for water and is easily dissolved in water, and the hydrophobic property is a property that has a low affinity for water and is difficult to dissolve in water. For example, as the hydrophilic block, ionic hydrophilicity such as sulfonic acid and sulfonate represented by the general formula (1), carboxylic acid and carboxylate represented by the general formula (2), etc. Examples thereof include a block segment containing a repeating unit structure having units. Moreover, although the structure containing many hydrophilic oxyethylene units and the repeating unit structure which has nonionic units, such as a hydroxyl group, etc. are mentioned, the hydrophilic block in the block polymer compound of this invention is not limited to these. Examples of the hydrophobic block include a repeating unit structure having a hydrophobic unit such as an isobutyl group, a t-butyl group, a phenyl group, a biphenyl group, and a naphthyl group, and the hydrophilicity in the block polymer compound of the present invention. The blocks are not limited to these.

  The following general formula (3) exemplifies a repeating unit structure preferably used as a block segment other than the general formulas (1) and (2), but is not limited thereto.

  General formula (3)

（式中、Ａは置換されていても良いポリアルケニル基を表す。Ｂ’は−Ｏ−、―ＯＣＯ―、―ＣＯＯ―、―ＣＯＮＲ^１―から選ばれる構造のうちのいずれかを表す。Ｒ^１は水素原子、または炭素原子数１から３までの直鎖状または分岐状の置換されていても良いアルキル基を表す。Ｄ’は炭素原子数１から１５までの直鎖状または分岐状の置換されていても良いアルキレン基を表す。また、ｍは０から３０までの整数を表し、ｍが複数の場合、それぞれのＤは異なっていても良い。Ｅ’は置換されていても良いアルキル基、アルキレン基、芳香族環または水素原子を表す。また、ｎ’は１から１０までの整数を表し、ｎ’が複数の場合、それぞれのＥ’は異なっていても良い。）

(In the formula, A represents an optionally substituted polyalkenyl group. B ′ represents any one of structures selected from —O—, —OCO—, —COO—, —CONR ¹ —. R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, which may be substituted, and D ′ is a linear or branched alkyl group having 1 to 15 carbon atoms. Represents an optionally substituted alkylene group, m represents an integer of 0 to 30, and when m is plural, each D may be different, and E ′ represents an optionally substituted alkyl. A group, an alkylene group, an aromatic ring or a hydrogen atom, and n ′ represents an integer of 1 to 10, and when n ′ is plural, each E ′ may be different.)

  As a specific example of the repeating unit structure represented by the general formula (3),

が挙げられるが、これらに限定されない。
（Ｐｈはフェニレンまたはフェニル基を表す。）

However, it is not limited to these.
(Ph represents a phenylene or phenyl group.)

  Each block segment of the block polymer of the present invention may be composed of a single repeating unit or may be composed of a plurality of repeating unit structures. Examples of the block segment composed of a plurality of repeating units include a random copolymer and a gradient copolymer whose composition ratio gradually changes. Further, the block polymer of the present invention is a block polymer having two or more block segments, and the block polymer may be a polymer obtained by graft bonding to another polymer.

  The block polymer compound of the present invention is a block polymer compound having two or more block segments. Examples of the block structure include the following. The present invention includes a diblock polymer AB, an ABA triblock polymer having the same block segment at both ends, a triblock polymer having different block segments, ABC, and those having other polymer units bonded to the triblock structure. For example, a polymer having four different block segments called ABCD, a model called ABCA, and a block polymer having a larger number of block segments are also included in the present invention. The block polymer compound of the present invention is characterized by having at least two block segments.

  In this invention, content of the repeating unit structure represented by General formula (1) contained in a high molecular compound is 0.01-99 mol% with respect to the whole high molecular compound, Preferably it is 1-90 mol%. A range is desirable. If it is 0.01 mol% or more and 99 mol% or less, the preferable polymer interaction which a sulfonic acid, a sulfonic acid ester, or a sulfonate should work is obtained.

  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 is 10000000 or less, there is little entanglement in the polymer chain and between the polymer chains, and the polymer chain is easily dispersed. If it is 200 or more, a preferable steric effect as a polymer can be obtained. 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 block polymer compound of the present invention preferably contains a polyalkenyl ether structure as a repeating unit structure. The content of the polyalkenyl ether structure is preferably 50 mol% or more. In general, a polymer compound having a polyalkenyl ether structure in the main chain has a low glass transition point Tg and flexible molecular mobility. In order to improve dispersion stability and inclusion (encapsulation), the molecular mobility of the block polymer is more flexible because it has a tendency to physically become entangled with the surface of the functional substance. Further, as described in detail later, it is also preferable that the coating layer is flexible in that a coating layer can be easily formed on the recording medium. Preferably, the glass transition temperature Tg of the main chain of the block polymer is 20 ° C. or lower, more preferably 0 ° C. or lower, and further preferably −20 ° C. or lower.

  Further, in the block polymer compound of the present invention, in response to stimulation, for example, from hydrophilic to hydrophobic or hydrophobic by stimulation such as temperature change, exposure to electromagnetic waves, pH change, concentration change, etc. It is also possible to include segments that cause a phase change from hydrophilic to hydrophilic. The block polymer compound of the present invention is a block polymer having at least two or more block segments, one of which is a repeating unit structure having a sulfonic acid derivative represented by the general formula (1), A block polymer compound characterized by being a copolymer composition with a repeating unit structure having a carboxylic acid derivative represented by the general formula (2), wherein the other one block segment contains a stimulus-responsive block segment. May be. The stimulus is preferably any one of temperature change, exposure to electromagnetic waves, change in pH, and change in concentration, and may be used in combination. It shows as a specific example of the block polymer compound of this invention which has a stimulus responsiveness. As a hydrophobic segment, shows a stimulus response to temperature,

を繰り返し単位構造として持ち、親水性セグメントとして、スルホン酸基を有する、

As a repeating unit structure, as a hydrophilic segment, having a sulfonic acid group,

の繰り返し単位構造と、カルボン酸基を有する、

A repeating unit structure having a carboxylic acid group,

の繰り返し単位構造との共重合体からなる、ＡＢジブロックポリマーが挙げられるが、これに限定されない。なお、前記疎水性セグメントは、温度の刺激に応答性を示すブロックセグメントであり、約２０℃以上で疎水性、それ以下で親水性を示し、ＤＳＣからも確認されている。

Examples include, but are not limited to, an AB diblock polymer composed of a copolymer with a repeating unit structure. The hydrophobic segment is a block segment that is responsive to temperature stimulation, exhibits hydrophobicity at about 20 ° C. or higher, and hydrophilic at lower temperatures, and has been confirmed by DSC.

The block polymer compound of the present invention is often polymerized by cationic polymerization, anionic polymerization, radical polymerization or the like. In the case of cationic polymerization, examples of the initiator include proton acids such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, perchloric acid, BF ₃ , AlCl ₃ , TiCl ₄ , SnCl ₄ , FeCl _3. , RAlCl ₂ , R _1.5 AlCl _1.5 (R represents alkyl), etc., a combination of a Lewis acid and a cation source (the cation source may be an adduct of protonic acid, water, alcohol, vinyl ether and sulfonic acid, etc. As an example. By causing these initiators to coexist with a polymerizable compound (monomer), the polymerization reaction proceeds and a block polymer compound can be synthesized.

The polymerization method that is more preferably used in the present invention will be described. A method for synthesizing a polymer containing a polyvinyl ether structure has been reported, but a method by cation living polymerization by Aoshima et al. (Polymer Bretan magazine, Vol. 15, page 417, JP-A-11-322942) is representative. . By conducting polymer synthesis by cation living polymerization, various polymers such as homopolymers and copolymers composed of two or more monomers, as well as block polymers, graft polymers, gradient polymers, etc., have a length (molecular weight). It can be accurately aligned and synthesized. In addition, living polymerization can also be carried out in a HI / I ₂ system, HCl / SnCl ₄ system, or the like.

  The polymer compound of the present invention is characterized in that it is a polymer compound obtained by copolymerizing a repeating unit structure having a sulfonic acid derivative and a repeating unit structure having a carboxylic acid derivative in the side chain. Polymer compounds obtained by copolymerizing repeating unit structures having different ionic functional groups of pKa can control the degree of dissociation of protons or cations of these ionic functional groups according to the difference in pH. Compared to a polymer compound having only a functional group, it is possible to form a higher-order and precise structure.

  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 polymer compound of the present invention. It contains a functional substance having a useful predetermined function, such as the above-described polymer compound and a coloring material, and the polymer compound can be suitably used to satisfactorily disperse the functional substance or the like. The functional substance is preferably a liquid or a solid, and may be a soluble substance. For example, oils, pigments, metals, herbicides, insecticides, biomaterials, drugs, dyes, molecular catalysts, and the like can be used.

  The polymer compound of the first invention contained in the polymer-containing composition of the present invention is 0.1 to 99% by mass, preferably 0.3%, based on the weight of the composition of the present invention. -70 mass%. When the amount is less than 0.1% by mass, the dispersibility of the functional substance may not be sufficient. When the amount exceeds 99% by mass, the viscosity may become too high. Moreover, content of the functional substance contained in the composition in this invention is 0.1 to 80 mass%. Preferably they are 0.5 mass% or more and 60 mass% or less. If it is 0.1 mass% or more, preferable functionality will be obtained, and if it is 80 mass% or less, preferable dispersibility will be obtained.

  Furthermore, the polymer-containing composition of the present invention contains a solvent and a dispersion medium, and a binder resin can be used as the dispersion medium. As the solvent or dispersion medium, water, an aqueous solvent, a non-aqueous organic solvent, or the like can be used. Of course, a mixture thereof can also be used.

  Examples of the aqueous solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin and other polyhydric alcohols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol. Polyhydric alcohol ethers such as monoethyl ether and diethylene glycol monobutyl ether, nitrogen-containing solvents such as N-methyl-2-pyrrolidone, substituted pyrrolidone and triethanolamine can be used. Moreover, monohydric alcohols, such as methanol, ethanol, and isopropyl alcohol, can also be used. As the non-aqueous organic solvent, hydrocarbon solvents such as hexane, heptane, octane, decane and toluene, and solvents such as cyclohexanone, acetone, methyl ethyl ketone and butyl acetate can be used. Natural oils such as olive oil, soybean oil, beef tallow, and pork fat can also be used. Examples of the binder resin include styrene acrylic copolymer and polyester.

  The content of the solvent and the dispersion medium in the polymer-containing composition of the present invention is 1% by mass or more and 99% by mass or less. Preferably they are 10 mass% or more and 95 mass% or less. If it is 1 mass% or more and 99 mass% or less, the preferable dispersibility of a functional substance will be acquired.

  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.

  In order to fully exhibit the said function, it is preferable to use the block polymer compound of this invention for the said high molecular compound, and it is still more preferable that the said block polymer compound is amphiphilic.

  The present invention, when the block polymer compound is used, characteristically contains a copolymer of a repeating unit structure having a sulfonic acid derivative having a small pKa and a repeating unit structure having a carboxylic acid derivative having a larger pKa. A block polymer compound is used. For this reason, it is possible to form a high-order and precise structure. For example, when the above-mentioned AB diblock polymer is used and a dispersion is prepared using water as a coloring material and a solvent, it is possible to enclose the coloring material in a micelle formed by the AB block polymer. It is also possible to form a color material-containing ink composition. Moreover, the particle diameter of the particles of the dispersion composition can also be made very uniform. Furthermore, the dispersion state can be made extremely stable, and the state of the dispersion composition and the degree of dissociation of protons or cations of ionic functional groups can be controlled by pH. For example, it is possible to increase the viscosity in the pH region where the carboxylic acid undergoes association and to lower the viscosity by dissociating the sulfonic acid or dissociating the carboxylic acid in other pH regions. Utilizing these characteristics, it can be used for pH sensors, pH sensitive materials, and the like. Further, when used as an ink composition, it can be stably dispersed in the image recording apparatus, and the image recording characteristics can be improved.

  One means for confirming the inclusion is to analyze this ink composition by instrumental analysis such as various electron microscopes and X-type diffraction. For example, EF-TEM observation by cryotransfer can be performed, spherical micelles can be observed, and inclusion of this sample can be confirmed by elemental analysis with EELS. In addition, the inclusion state can be indirectly confirmed by separating the colorant from the solvent separately from the polymer under the micelle collapse condition. For example, it becomes possible by using the block segment that can change the phase of the lyophobic medium as described above as a lyophobic segment of the present invention. Using this, an ink containing a color material insoluble in a solvent is created, and the phase is changed from a lyophobic segment to a lyophilic segment by stimulation. As a result, it can be used as a means for confirming the inclusion.

  Furthermore, an ink composition which is a preferred embodiment of the composition of the present invention will be described.

  The content of the block polymer compound of the first invention of the present invention contained in the ink composition of the present invention is used in the range of 0.1 to 90% by mass. Preferably they are 0.3 mass% or more and 80 mass% or less. For an inkjet printer, it is preferably used in an amount of 0.3 to 30% by mass.

  Next, components other than the block polymer compound contained in the ink composition of the present invention will be described in detail. Other components include water, aqueous solvents, coloring materials, additives, and the like. Those examples are the examples described above.

  Representative examples of the color material include pigments and dyes. 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. Moreover, you may use together with dye.

  The following are examples of commercially available pigments for black, cyan, magenta, and yellow.

  Examples of black pigments include Raven 1060 (trade name, manufactured by Colombian Carbon), MOGUL-L (trade name, manufactured by Cabot), Color Black FW1 (trade name, manufactured by Degussa), MA100 (trade name, Mitsubishi Chemical). However, it is not limited to these.

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

  Examples of magenta pigments include C.I. I. Pigment Red-122, C.I. I. Pigment Red-123, C.I. I. Pigment Red-146 and the like, but are not limited thereto.

  Examples of yellow pigments include C.I. I. Pigment Yellow-74, C.I. I. Pigment Yellow-128, C.I. I. Pigment Yellow-129 and the like, but are not limited thereto.

  In the ink composition of the present invention, a pigment that is self-dispersible in water can also be used. Examples of water-dispersible pigments include those using a steric hindrance effect in which a polymer is adsorbed on the pigment surface and those using electrostatic repulsion, and commercially available products include CAB-0-JET200, CAB- Examples include 0-JET300 (trade name, manufactured by Cabot Corporation), Microjet Black CW-1 (trade name, manufactured by Orient Chemical Co., Ltd.), and the like. The pigment used in the ink composition of the present invention is preferably 0.1 to 50% by mass with respect to the total weight of the ink composition. When the amount of the pigment is 0.1% by mass or more, a preferable image density is obtained, and when it is 50% by mass or less, preferable dispersibility is obtained. A more preferable range is 0.5 to 30% by mass.

  A dye can also be used in the ink composition of the present invention. Direct dyes, acid dyes, basic dyes, reactive dyes, water-soluble dyes for foodstuffs, insoluble dyes such as oil-soluble dyes or disperse dyes can be used as described below.

  For example, water-soluble dyes include C.I. I. Direct black, -17, -62, -154; I. Direct yellow, -12, -87, -142; I. Direct Red, -1, -62, -243; I. Direct blue, -6, -78, -199; C.I. I. Direct orange, -34, -60; C.I. I. Direct violet, -47, -48; C.I. I. Direct Brown, -109; C.I. I. Direct dyes such as direct green and -59, C.I. I. Acid Black, -2, -52, -208; C.I. I. Acid Yellow, -11, -29, -71; C.I. I. Acid Red, -1, -52, -317; I. Acid Blue, -9, -93, -254; C.I. I. Acid Orange, -7, -19; C.I. I. Acid violet, acidic dyes such as -49, C.I. I. Reactive black, -1, -23, -39; I. Reactive yellow, -2, -77, -163; I. Reactive red, -3, -111, -221; I. Reactive Blue, -2, -101, -217; C.I. I. Reactive orange, -5, -74, -99; C.I. I. Reactive violet, -1, -24, -38; I. Reactive Green, -5, -15, -23; C.I. I. Reactive dyes such as reactive brown, -2, -18 and -33, C.I. I. B. Basic Black, -2; I. B. Basic Red, -1, -12, -27; I. Basic blue, -1, -24, C.I. 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.

  The dye used in the ink composition of the present invention is preferably 0.1 to 50% by mass with respect to the total weight of the ink composition. A more preferable range is 1 to 40% by mass. In addition, although the example of these said coloring material is preferable with respect to the ink composition of this invention, the coloring material used for the ink composition of this invention is not specifically limited to the said coloring material.

  As the solvent, any of water, an aqueous solvent, and an organic solvent can be used, but water is preferably used. As water, ion-exchanged water, pure water and ultrapure water from which metal ions and the like have been removed are preferable.

  Water is preferably contained in the ink composition of the present invention in an amount of 1 to 95% by mass. More preferably, it is contained less than 5 to 90% by mass. In the range of 1 to 95% by mass, the effect of dispersion is more remarkable, and a more uniform dispersion state of the functional substance can be realized.

  Examples of the aqueous solvent include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and 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, monohydric alcohols such as methanol, ethanol, and isopropyl alcohol can be used for the purpose of accelerating the drying on paper (recording medium).

  The aqueous solvent is preferably contained in the ink composition of the present invention in an amount of 0.1 to 50% by mass. More preferably, it is contained less than 0.5 to 40% by mass. In the range of 0.1 to 50% by mass, the wetting effect is more remarkable, and a more uniform dispersion state of the functional substance can be realized.

  The content of the block polymer contained in the ink composition of the present invention is 0.1 to 90% by mass, preferably 0.3 to 80% by mass with respect to the total weight. When the amount of the block polymer is less than 0.1% by mass, the pigment contained in the ink composition of the present invention may not be sufficiently dispersed, and when it exceeds 90% by mass, the viscosity may be excessively increased. is there.

  The ink composition of the present invention is preferably used as an inkjet ink.

  Next, a method for producing an inkjet ink in the present invention will be described.

[Inkjet ink creation method]
As a method for preparing the ink composition for inkjet of the present invention, a pigment, the block polymer compound of the present invention, an additive and the like are added to ion-exchanged water, dispersed using a disperser, and then coarsely processed by a centrifugal separator or the like. An example of removing particles, then adding water or a solvent and an additive, and performing stirring, mixing, and filtration can be given.

  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.

  Even when a self-dispersing pigment is used, it can be prepared by the same operation as the above method.

  The ink composition of the present invention can also be applied to a toner composition. This will be described below.

[Toner composition]
Specifically, the toner composition of the present invention contains a dispersion medium such as a binder resin, a color material, and the above-described polymer compound of the present invention.

  The content of the polymer compound of the present invention contained in the toner composition of the present invention can be in the range of 0.1 wt% to 90 wt%. Here, it is preferably 0.5 wt% or more and 80 wt% or less.

  Further, the polymer compound of the present invention can be used as a binder resin itself, or can be used together with a binder resin such as a styrene acrylic resin or a polyester resin.

  Next, components other than the polymer compound contained in the toner composition of the present invention will be described in detail. Other components can include a binder resin, a color material (pigment, dye), a charge control agent, a release agent, an external additive, magnetic particles, and the like.

  Examples of the binder resin include styrene acrylic copolymer, polyester, polycarbonate, and the like. The content of the binder resin is preferably 10% by mass or more and 99% by mass or less.

  As the color material, pigments and dyes described in the description of the ink composition can be used. The content of the color material is used in the range of 0.1% by mass to 50% by mass. Examples of the charge control agent include metal-azo complexes, triphenylmethane dyes, nigrosine, ammonium salts and the like. The charge control agent is used in an amount of 0.1% by mass to 30% by mass.

  Other examples of the release agent include synthetic wax and natural wax.

  Examples of the external additive include inorganic fine particles such as silica, alumina and titania, and resin fine particles such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene.

  Examples of magnetic particles include magnetite, hematite, and ferrite.

  The toner composition of the present invention may function even if it does not necessarily contain all of the above components, and may contain components not described above.

  Examples of the method for producing the toner composition of the present invention include the following methods. For example, the above-described constituent components are mixed, melted and blended, uniformly mixed, then crushed with a speed mill or jet mill, and sized to obtain a toner of a desired size. A toner composition can be produced by adding an external additive to the toner and mixing with a mixer.

  Next, the liquid application method of the present invention will be described.

[Liquid application method and image forming method]
The ink composition of the present invention can be used in various image forming methods and apparatuses such as various printing methods, ink jet methods, and electrophotographic methods, and can be drawn by an image forming method using this device. Moreover, when using a liquid composition, it can be used for the liquid provision method for forming a fine pattern in the inkjet method etc. or administering a medicine.

  The image forming method of the present invention is a method for forming an excellent image with the composition of the present invention. The image forming method of the present invention is preferably an image forming method in which recording is performed by discharging the ink composition of the present invention from an ink discharge portion and applying the ink composition onto a recording medium.

  The ink jet method used may be a known method such as a piezo ink jet method using a piezoelectric element or a bubble jet (registered trademark) method in which thermal energy is applied to ink to perform 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.

  The present invention also includes a liquid application method for fixing the ink composition on a recording medium by bringing the ink composition into contact with a substance or composition that changes the pH of the ink composition. Various methods can be applied to the method of applying the substance or composition for changing the pH. For example, as described in JP-A-64-63185, a polyvalent cation can be implanted over the entire area where an image is formed by an inkjet head. It is also preferable to apply a polyvalent cation to the recording medium in advance.

  Next, the image forming apparatus of the present invention will be described.

[Liquid applicator]
The ink composition of the present invention includes a liquid applying apparatus using the liquid applying method, a pattern forming apparatus using a pattern forming method for forming a certain pattern on a recording medium, and images and characters on the recording medium. It can be used in an image forming apparatus using various image forming methods such as various printing methods, ink jet methods, and electrophotographic methods, and is particularly preferably used in an ink jet recording device.

  The inkjet recording apparatus using the inkjet ink of the present invention is an inkjet recording apparatus such as a piezo inkjet system using a piezoelectric element or a bubble jet (registered trademark) system in which thermal energy is applied to ink to perform recording. including.

  FIG. 1 is a schematic functional diagram of the ink jet recording apparatus. Reference numeral 50 denotes a central processing unit (CPU) of the inkjet recording apparatus 20. 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 thereof, 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 drive circuit 60 transmits a signal to the head 70 for discharging various ink compositions (Y, M, C, K) or stimulus stimulating substances 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

(Synthesis Example 1)
<Synthesis of block polymer>
Random copolymer of isobutyl vinyl ether (IBVE: A block), methyl 4- (2-vinyloxyethoxy) benzenesulfonate and ethyl 4- (2-vinyloxyethoxy) benzoate (VEOEtPhSO ₃ Me-r-VEOEtPhCOOEt: B Synthesis of diblock polymer consisting of block).

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

Next, a toluene solution of B block VEOEtPhSO ₃ Me 1.5 mmol (mmol) and VEOEtPhCOOEt 1.5 mmol was added to continue the polymerization. As a result of monitoring using GPC, the polymerization reaction was stopped when the polymerization was completed with about half of the B block. 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, and the target product A block polymer was obtained. The compound was identified using NMR and GPC. Mn = 19500 and Mw / Mn = 1.31. The polymerization ratio was A: B = 200: 15. The polymerization ratio of the two monomers in the B block was approximately 1: 1.

  Furthermore, the block polymer obtained here was hydrolyzed in a mixed solution of dimethylformamide and sodium hydroxide, and the B block component was hydrolyzed to obtain a triblock polymer that was sodium chloride. The compound was identified using NMR and IR.

  Further, neutralization was performed with 0.1N hydrochloric acid in an aqueous dispersion to obtain a diblock polymer in which the B component became free sulfonic acid or carboxylic acid. The compound was identified using NMR and GPC.

(Synthesis Example 2)
2- (4-methylbenzeneoxy) ethyl vinyl ether (TolOVE: A block), 2-methoxyethoxyethyl vinyl ether (MOEOVE: B block), methyl 4- (2-vinyloxyethoxy) benzenesulfonate and 4- ( Synthesis of a triblock polymer composed of a random copolymer of 2-vinyloxyethoxy) ethyl benzoate (VEOEtPhSO ₃ Me-r-VEOEtPhCOOEt: C block).

In the same manner as in Synthesis Example 1, 20 mmol of IBVE of A block described in Synthesis Example 1 is replaced with 10 mmol of TolOVE, and 4.5 mmol of MOEOVE is added at the completion of polymerization of A block, and VEOEtPhSO of C block at the completion of polymerization of B block A toluene solution of 1.5 mmol of ₃ Me and 1.5 mmol of VEOEtPhCOOEt was added for polymerization to obtain a target triblock polymer. Identification of the compound of the triblock polymer was performed using NMR and GPC. Mn = 21400 and Mw / Mn = 1.28. The polymerization ratio was A: B: C = 100: 45: 15. The polymerization ratio of the two types of monomers in the C block was about 1: 1.

  Further, a triblock polymer in which the C component was a free carboxylic acid was obtained in the same manner as in Synthesis Example 1.

(Example 1)
15 parts by mass of the sulfonate-carboxylate type diblock polymer obtained in Synthesis Example 1 and 7 parts by mass of Oil Blue N (trade name, CI Solvent Blue-14; manufactured by Aldrich) were added to dimethylformamide. The ink composition was co-dissolved in 150 parts by mass and converted into an aqueous phase using 400 parts by mass of water to obtain an ink composition. After standing for 10 days, oil blue did not separate and precipitate.

(Example 2)
15 parts by mass of the sulfonate-carboxylate type triblock polymer obtained in Synthesis Example 2 and 7 parts by mass of Oil Blue N (trade name, CI Solvent Blue-14; manufactured by Aldrich) were added to dimethylformamide. The ink composition was co-dissolved in 150 parts by mass and converted into an aqueous phase using 400 parts by mass of water to obtain an ink composition. After standing for 10 days, oil blue did not separate and precipitate.

(Example 3)
When the ink produced in Example 2 was filled in the print head of an inkjet printer (trade name, BJF800; manufactured by Canon Inc.) and a 30 mm × 30 mm square was printed with a solid, it was possible to print uniformly. After 1 minute of printing, the printed part was rubbed 3 times with a line marker, but it was found that there was no blue blur and the fixing property was very good. Further, when water was dripped onto the printing portion, it was found that there was no bleeding and the water resistance was very good.

(Comparative Example 1)
Black self-dispersion pigment (trade name CAB-0-JET300, manufactured by Cabot Corporation) 2 parts by mass, surfactant (Nonion E-230, manufactured by NOF Corporation) 0.5 parts by mass, ethylene glycol 5 parts by mass, and ions 92.5 parts by mass of exchange water was mixed to prepare an ink composition. Using this ink composition, printing was carried out in the same manner as in Example 3. One minute after printing, the printed part was strongly rubbed once with a line marker, and black blotting was observed.

(Comparative Example 2)
15 parts by mass of a diblock polymer of styrene-b-styrenesulfonic acid (Mn = 22800, Mw / Mn = 1.33, polymerization ratio 150: 50) and oil blue N (CI Solvent Blue-14, manufactured by Aldrich) ) 7 parts by mass was dissolved in 150 parts by mass of dimethylformamide and converted into an aqueous phase using 400 parts by mass of water to obtain an ink composition.

  Printing was performed in the same manner as in Example 3 using the ink composition. When water was dripped onto the printed part, bleeding was observed.

(Comparative Example 3)
15 parts by mass of diblock polymer of styrene-b-acrylic acid (Mn = 18200, Mw / Mn = 1.20, polymerization ratio 150: 50) and oil blue N (trade name, CI Solvent Blue-14; Aldrich 7 parts by mass) were co-dissolved in 150 parts by mass of dimethylformamide and converted into an aqueous phase using 400 parts by mass of water to obtain an ink composition.

  When printing was performed in the same manner as in Example 3 using the ink composition, faintness (a portion not printed) was confirmed.

Example 4
The pH 12 ink composition prepared by the same procedure as in Example 2 was printed on plain paper previously sprayed and dried with an aqueous hydrochloric acid solution of pH 4 using the same ink jet printer as in Example 3. The obtained print was uniform. One minute after printing, the printed part was rubbed 5 times with a line marker, but it was found that there was no blue blur and the fixing property was very good. Further, when water was dripped onto the printing portion, it was found that there was no bleeding and the water resistance was very good.

(Example 5)
Using the sulfonic acid type-carboxylic acid type triblock polymer obtained in Synthesis Example 2, a toner composition was prepared as follows.

100 parts by mass of polyester resin (bisphenol A, terephthalic acid, n-dodecenyl succinic acid, trimellitic acid, diethylene glycol synthesized in molar ratio 20: 38: 10: 5: 27), 70 parts by mass, magnetite (Fe ₃ O ₄ ), After preliminarily mixing 2 parts by mass of the triblock polymer, 2 parts by mass of triphenylmethane dye, and 3 parts by mass of low molecular weight polypropylene, the mixture was melt-kneaded with a ruder. This was cooled, coarsely pulverized with a speed mill, finely pulverized with a jet mill, and further classified with a zigzag classifier to obtain a toner having a volume average diameter of 11 μm.

  100 parts by mass of this toner was treated with amino-modified silicone oil (viscosity at 25 ° C., 100 cp, amine equivalent 800) 0.4 parts by mass of positively charged hydrophobic dry silica and spherical PVDF particles having an average particle size of 0.2 μm. 2 parts by mass were added and mixed with a Henschel mixer to obtain a positively chargeable toner composition. When this toner composition was used and printing was performed with a Canon Copier NP-3525, fine printing was possible.

(Example 6)
30 parts by mass of the sulfonic acid type-carboxylic acid type triblock polymer obtained in Synthesis Example 2 was dissolved in 150 parts by mass of THF (tetrahydrafuran), and converted to an aqueous phase using 400 parts by mass of NaOH aqueous solution. , 9, 11, and 12 were prepared and their respective viscosities were measured. As a result, the maximum viscosity was obtained from the low pH to the high pH region.

pH viscosity (cps)
7 5.9
9 12.2
11 8.5
12 3.7
(Example 7)
15 parts by mass of a sulfonate type-carboxylate type triblock polymer obtained in Synthesis Example 2 and C.I. I. 7 parts by weight of Pigment Blue 15: 3 was put into 400 parts by weight of NaOH aqueous solution adjusted to pH 9 and stirred at high speed using a process homogenizer PH91 (manufactured by SMT) (3 hours). Depending on the direct dispersion here, the viscosity of the dispersion solution was increased by increasing the viscosity under weak alkaline conditions, and an ink composition with extremely good stability was obtained. The viscosity was 15.2 cps. Dialysis was performed using a semipermeable membrane of cellulose to remove excess NaOH to obtain an ink composition having a pH of 7. The viscosity was 4.7 cps. After standing for 10 days, no pigment precipitation was observed.

  Using this ink composition, printing was performed in the same manner as in Example 3. After 1 minute of printing, the printed part was rubbed with a line marker three times, but it was found that there was no blue blur and the fixing property was very good. . Further, when water was dripped onto the printing portion, it was found that there was no bleeding and the water resistance was very good.

1 is a diagram illustrating a schematic mechanism of an image forming apparatus of the present invention.

Claims (14)

A polymer compound comprising a repeating unit structure represented by the following general formula (1) and a repeating unit structure represented by the following general formula (2) as a copolymer composition.
General formula (1)

(In the formula, A represents an optionally substituted polyalkenyl group. B represents any one of structures selected from —O—, —OCO—, —COO—, —CONR ¹ —, —CH ₂ —. R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, which may be substituted, and D is a straight chain having 1 to 15 carbon atoms or A branched alkylene group which may be substituted, a methylene group in the alkylene group may be substituted with an oxygen atom or an aromatic ring, and m represents an integer of 0 to 30; In a plurality of cases, each D may be different, E represents an optionally substituted aromatic ring, n represents an integer from 0 to 10, and when n is a plurality, each E May be different, and m + n ≧ 1. .R is ^{_{-SO 3 H, -SO 3 R 2}} , represents a _-SO 3 -M .R ² is a linear or branched optionally substituted alkyl group having 1 to 5 carbon atoms, Or an aromatic ring which may be substituted; M represents a monovalent or polyvalent cation.)
General formula (2)

(In the formula, A represents an optionally substituted polyalkenyl group. B represents one of structures selected from —O—, —OCO—, —COO—, and —CONR ¹ —. R ¹ Represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and D represents a linear or branched substituted group having 1 to 15 carbon atoms. An methylene group in the alkylene group may be substituted with an oxygen atom or an aromatic ring, m represents an integer of 0 to 30, and when m is plural, D may be different, E ′ represents an optionally substituted alkyl group or an aromatic ring, and n ′ represents an integer of 1 to 10, and when n ′ is plural, E ′ may be different, R ′ may be —COOH. -COOR ^2, .M .R ² is representing a linear or branched optionally substituted alkyl group or an aromatic ring having 1 to 5 carbon atoms that represents a -COO-M is a monovalent or Represents a polyvalent cation, and 1 is one or more.) The polymer compound is a block polymer having at least two or more block segments;
The copolymer composition of the repeating unit structure represented by the general formula (1) and the repeating unit structure represented by the general formula (2) is contained in at least one block segment of the block polymer. The polymer compound according to claim 1.   The polymer compound according to claim 2, wherein the polymer compound is amphiphilic.   The polymer compound according to claim 1, wherein the repeating unit structure contains a polyalkenyl ether structure.   A polymer-containing composition comprising the polymer compound according to any one of claims 1 to 4, a solvent or a dispersion medium, and a functional substance.   The polymer-containing composition according to any one of claims 2 to 5, wherein the functional substance is included in the polymer compound.   7. The ink composition according to claim 5, wherein the functional substance is a color material.   The ink composition according to claim 7, wherein the ink composition is used for a toner.   An ink application method comprising the step of applying the ink composition according to claim 7 to a medium.   The ink application method according to claim 9, wherein the ink composition is brought into contact with a substance or a composition that changes the pH of the ink composition.   The ink application method according to claim 10, wherein a substance or a composition that changes the pH of the ink composition is provided in advance on the medium.   An image forming method comprising applying the ink composition according to claim 7 to a medium to form an image. Ink application means for applying energy to the medium by applying energy to the ink composition according to claim 7;
An ink applying apparatus comprising: a driving unit for driving the ink applying unit.   A medium for forming an image by applying an ink composition, wherein the medium comprises a substance or a composition that changes the pH of the ink composition by contact with the ink composition. Medium.

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