JP2009013269A - Actinic ray-curable liquid composition and liquid cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an actinic ray-curable liquid composition excellent in solubility with water, curing property with actinic rays and stability when used for the forming material of aqueous ink. <P>SOLUTION: The actinic ray-curable liquid composition contains a compound expressed by structural formula (I). In the formula, A represents H or OH; R<SB>1</SB>represents a divalent group; E represents an amide coupling; R<SB>n</SB>represents a cyclic connecting group; m is 0 or more and n is 2 or more satisfying m+n=3; and Z represents a triazine ring. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel active energy ray-curable liquid composition represented by a photocurable inkjet ink, and a liquid cartridge including the same.

  Conventionally, there is a method in which a liquid composition is applied onto a recording medium, and a curable substance in the liquid composition is cured by irradiating light containing active energy rays to form a cured film to form an image. Are known. For example, a non-aqueous active energy ray-curable substance is emulsified and dispersed in an aqueous vehicle, and a liquid composition (curable emulsion paint) added with a coloring material is applied to a medium. It is the kind of technology that forms.

  In recent years, such active energy ray-curable liquid compositions and various paints using them have been widely applied to graphic arts, sign art, display panel manufacturing, label recording, package recording, and production of electronic circuit boards. ing.

  Among them, a technique for applying a liquid composition containing such an active energy ray-curable substance as an ink to an ink jet recording method is known. When an active energy ray-curable liquid composition is used in such an ink jet recording method, it is conceivable to apply a non-aqueous or aqueous curable substance as the curable substance used therefor. In the case of using a non-aqueous curable substance, it is roughly divided into two types. One of them is a so-called oil-based ink in which a pigment is dispersed in an organic solvent such as toluene or methyl ethyl ketone. Another type is a so-called 100% curable ink (non-solvent ink) that does not use the organic solvent as described above and contains a liquid monomer, oligomer, and pigment dispersion.

  However, when using the oil-based ink as described above, since the organic solvent is easily volatilized in the atmosphere, sufficient consideration for the environment is necessary. In addition, the 100% curable ink is required to have all the ink components applied on the recording medium as a cured film, so that irregularities are likely to occur between the recording portion and the non-recording portion, and it is difficult to obtain a glossy image. . For this reason, it is difficult to develop applications for which high image quality is required.

  On the other hand, when applying a water-based curable substance, since the aqueous solvent which has water as a main component is used as a solvent, the environmental impact by volatilization of a solvent is comparatively small. In addition, it is possible to suppress the occurrence of unevenness like 100% curable ink. For these reasons, a technique using an active energy ray-curable liquid composition to which an aqueous curable material is applied in an inkjet recording method is extremely useful. Under such circumstances, development of an aqueous active energy ray-curable liquid composition and development of various hydrophilic reactive resins applicable to it have been demanded.

  Under these circumstances, as an example of the aqueous active energy ray-curable material, one of hydrophilic curable materials having both an acidic group and a (meth) acryloyl group or a vinyl group is known. Examples of such a material include an ester of succinic anhydride and 2-hydroxyethyl (meth) acrylate, an ester of orthophthalic anhydride and 2-hydroxyethyl (meth) acrylate, vinyl naphthalenesulfonic acid, and the like. .

  As another example, as a compound that is soluble in water, has two or more polymerizable functional groups in one molecule, and is industrially produced, a hydrophilic property is imparted by a polyethylene oxide chain. Sexual substances are known. Examples of such include (meth) acrylic acid esters of polyhydric alcohols such as diethylene glycol di (meth) acrylate and tetraethylene glycol di (meth) acrylate.

  Patent Document 1 discloses a polyfunctional hydrophilic curable substance. The compound disclosed here is used for the purpose of increasing the number of hydroxyl groups in a molecule as a method for imparting hydrophilicity.

  Patent Documents 2 and 3 disclose (meth) acrylic acid ester of hydrophilic polyepoxide derived from polyalcohol. The compounds disclosed in these documents are satisfactory to some extent in the curability by active energy rays and the physical properties of the cured product, and the viscosity when the compound is used as an aqueous solution also satisfies the level required for inkjet inks. It is.

  Furthermore, Patent Document 4 discloses an energy ray-curable powder coating composition having an ethylenically unsaturated group-containing compound in addition to a spiro ring-containing (meth) acrylate compound.

JP-A-8-165441 JP 2000-117960 A JP 2002-187918 A JP 2003-165927 A

  However, in some cases, the compounds described in the conventional techniques as described above are not sufficient as a main material of the active energy ray-curable liquid composition applicable to the ink jet recording method. For example, a compound having one polymerizable functional group in one molecule has only one polymerizable functional group in one molecule, so the polymerization rate is slow and the degree of crosslinking of the cured film is low. There are many. For this reason, in view of the recent demand for higher durability, liquid compositions to which these are applied are generally inferior in curability and cured film properties, and are not likely to be the main materials targeted by the present invention.

  Further, according to the study by the present inventors, a compound that is soluble in water, has two or more polymerizable functional groups in one molecule, and is industrially produced is as follows. It turned out that there was such a problem. That is, these compounds are poor in water solubility when the ethylene oxide chain is short, and conversely, when the ethylene oxide chain is long, water solubility is obtained, but the cured film properties, particularly, various properties such as hardness, adhesion, and stickiness are not sufficient. There is a case.

  In addition, the compound described in Patent Document 1 described above has water solubility and can be cured by active energy rays, but its use is an ink receiving layer for a recording medium. It is unknown whether it can be applied to the problem. Further, according to the study by the present inventors, when these compounds are contained, there is a problem that, when a liquid composition is used, the viscosity tends to increase and the range of application is limited.

  Further, according to the study by the present inventors, the compounds such as (meth) acrylic acid ester of hydrophilic polyethylene oxide described in Patent Documents 2 and 3 described above have the following problems. That is, when such an aqueous curable substance having a (meth) acrylic acid ester group is used as a material for an aqueous ink, the following may occur. As coloring materials for water-based inks, in general, dyes that are dissolved in an aqueous medium by an anionic group and pigment dispersions in which a pigment is dispersed in an aqueous medium by an anionic group are used. On the other hand, when the water-based curable substance as described above is contained in the water-based ink, the pH of the liquid composition is lowered to an acidic region as acrylic acid is generated by hydrolysis of the (meth) acrylic acid ester group. There is. In such a state, the original pH is adjusted in the alkali to neutral region, the dye that was originally stably present in the ink is precipitated, the aggregation or sedimentation of the pigment dispersion occurs, There may be a problem in terms of the storage stability of the water-based ink. Furthermore, it is particularly noticeable in the ink jet recording method in which ink is ejected by the action of thermal energy, but the curable substance in the ink generates an insoluble matter due to an unexpected reaction, causing a problem in terms of ejection stability. There is also.

  Moreover, the use of the compound described in Patent Document 4 is a powder coating composition, and it is unclear whether the compound can be applied to a liquid composition or is water-soluble. Furthermore, since it is described that a monofunctional maleimide compound or the like is preferable, it is not clear whether sufficient curability can be obtained.

Accordingly, the first object of the present invention is to provide an active energy ray-curable liquid containing a compound having excellent water solubility, active energy ray curability, stability when used as a water-based ink forming material, and the like. It is to provide a composition. Specifically, it contains a compound that exhibits sufficient water-solubility, cures quickly and sufficiently with active energy rays, and the formed cured product has the following excellent characteristics, and also has stability against heat and storage. It is an object to provide an active energy ray-curable liquid composition excellent in. A cured product formed by the active energy ray-curable liquid composition has excellent strength and adhesion, and excellent fixability and marker resistance.
In addition, the second object of the present invention is to have the above-described effects and high practical value by using the above-described active energy ray-curable liquid composition and including a liquid storage portion that stores the active energy ray-curable liquid composition. It is to provide a liquid cartridge.

（上記（Ｉ）において、Ａは水素原子、水酸基又は置換基を有していてもよい１価の有機残基を表し、Ｒ₁は置換基を有していてもよい２価の有機基を表し、Ｅはアミド結合を表し、Ｒ_nはカルボニル基と該カルボニル基の炭素原子に隣接した不飽和炭素−炭素結合を有する環状連結基を表し、ｍは０以上の数を表し、ｎは２以上の数を表し、かつ、ｍ＋ｎ＝３である。またＺはトリアジン環を有する構造を表す。） The above object is achieved by the present invention described below. That is, as the first embodiment of the present invention, there is provided an active energy ray-curable liquid composition comprising a compound represented by the following structural formula (I).

(In the above (I), A represents a hydrogen atom, a hydroxyl group or a monovalent organic residue which may have a substituent, and R ₁ represents a divalent organic group which may have a substituent. E represents an amide bond, R _n represents a cyclic linking group having a carbonyl group and an unsaturated carbon-carbon bond adjacent to the carbon atom of the carbonyl group, m represents a number of 0 or more, and n represents 2 And the number is m + n = 3, and Z represents a structure having a triazine ring.)

また、上記構成を有する本発明においては、前記構造式（Ｉ）中のＲ₁が、置換基を有していてもよい炭素数１から６のアルキレン基であることが好ましい。
また、上記構成を有する本発明においては、前記構造式（Ｉ）中のＲ_nが、下記構造式（VI）、（VII）及び（VIII）のいずれかで表される構造であることが好ましい。

また、上記構成を有する本発明においては、構造式（Ｉ）で示される化合物の水溶性が、２５℃・１気圧下の純水に対し１質量％以上溶解するものであることが好ましい。 In the present invention having the above-described structure, A in the structural formula (I) is a structure represented by any of the following (II), (III), (IV) and (V): preferable.

In the present invention having the above structure, R ₁ in the structural formula (I) is preferably substituted alkylene group having carbon atoms 1 six.
In the present invention having the above structure, R _n in the structural formula (I) is preferably a structure represented by any of the following structural formulas (VI), (VII), and (VIII). .

Moreover, in this invention which has the said structure, it is preferable that the water solubility of the compound shown by structural formula (I) melt | dissolves 1 mass% or more with respect to the pure water under 25 degreeC * 1 atmosphere.

  Furthermore, as a second embodiment of the present invention, there is provided a liquid cartridge comprising a liquid storage portion that stores any one of the above active energy ray-curable liquid compositions.

According to the first aspect of the present invention, an active energy ray-curable liquid composition excellent in various performances can be provided. In particular, it is possible to provide an aqueous active energy ray-curable liquid composition that is extremely excellent in water solubility, curability, stability, and the like. For this reason, a liquid composition excellent in ejection stability and storage stability that can be suitably applied to an inkjet recording method is provided, and the formation of an image excellent in fixability and marker resistance is stably performed. Is possible.
In addition, according to the second aspect of the present invention, there is provided a liquid cartridge having a high practical value, comprising a liquid storage portion in which the active energy ray-curable liquid composition capable of achieving the above-described excellent effects is stored. be able to.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. Of course, the scope of the present invention is not limited to this example. As a result of intensive studies, the present inventors have found an active energy ray-curable liquid composition containing a compound represented by the following structural formula (I). For the first time, the present inventors have found that a remarkable effect that cannot be easily anticipated appears for the purpose, and have achieved the present invention. That is, the compound is water-soluble, has excellent curability by active energy rays, and has excellent stability even when used as a water-based ink forming material. Furthermore, the cured product formed by the compound is excellent in strength and adhesion, and excellent in fixability and marker resistance. In addition, when the compound is contained to form a liquid composition such as a water-based ink, the liquid composition has excellent stability against heat and storage, as well as the above-mentioned characteristics. It becomes. In the present invention, that the compound is water-soluble means that 1% by mass or more is dissolved in pure water at 25 ° C. and 1 atm.

（上記（Ｉ）において、Ａは水素原子、水酸基又は置換基を有していてもよい１価の有機残基を表し、Ｒ₁は置換基を有していてもよい２価の有機基を表し、Ｅはアミド結合を表す。また、Ｒ_nはカルボニル基と該カルボニル基の炭素原子に隣接した不飽和炭素−炭素結合を有する環状連結基を表し、ｍは０以上の数を表し、ｎは２以上の数を表し、かつ、ｍ＋ｎ＝３である。また、Ｚはトリアジン環を有する構造を表す。）

(In the above (I), A represents a hydrogen atom, a hydroxyl group or a monovalent organic residue which may have a substituent, and R ₁ represents a divalent organic group which may have a substituent. E represents an amide bond, R _n represents a carbonyl group and a cyclic linking group having an unsaturated carbon-carbon bond adjacent to the carbon atom of the carbonyl group, m represents a number of 0 or more, and n Represents a number of 2 or more and m + n = 3, and Z represents a structure having a triazine ring.

  This active energy ray-curable liquid composition was applied to an ink jet recording method, and its ejection stability and cured film were evaluated. As a result, the polymerization rate and the degree of crosslinking of the cured film were sufficient, the cured film was less sticky, the formation of insoluble matter due to unexpected reactions was within an acceptable range, the pH change was small and the storage stability was good. . That is, it was confirmed that the active energy ray-curable liquid composition exhibits extremely excellent overall performance.

  The reason why such an excellent performance is manifested by the above-described configuration is not clear, but the present inventors presume as follows. First, it is water-soluble, but the amide bond of this compound is hydrophilic, and the triazine ring, which is the parent of this compound, can be substituted with a hydrophilic group other than a polymerizable functional group. I guess that.

Moreover, it is speculated that the good curability was expressed due to the following structural characteristics of the compound represented by the structural formula (I). First, the compound is unsaturated carbon adjacent to the carbon atom of the carbonyl group and the carbonyl group - has an annular linking group R _n having carbon bond. In addition, the structure has polymerizability, it is polyfunctional, and the crosslink density tends to increase structurally, and a dense cured film tends to be formed.

  Furthermore, the stability in the case of using water-based ink is estimated as follows. The compound represented by the structural formula (I) does not have a relatively poor bonding mode (for example, an acrylate group) inside the compound, and the amount of acid generated by hydrolysis of the compound is extremely small. Is presumed to be a factor. Furthermore, since the parent of this compound is a heterocyclic triazine ring, it is presumed that there are few factors such as thermal precipitation and decomposition.

Details of preferred examples of the compound represented by the structural formula (I) will be described below in detail. According to studies by the present inventors, in the present invention having the above-described configuration, A in the structural formula (I) is represented by any one of the following (II), (III), (IV) and (V). This is a desirable form. Among these, when A in the structural formula (I) is a structure represented by the following (III), the water solubility of the compound can be particularly improved.

Further, according to the study by the present inventors, in the present invention having the above structure, R ₁ in the structural formula (I) is an alkylene group having 1 to 6 carbon atoms which may have a substituent. It is a desirable form. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

Furthermore, as an example of a remarkably preferable form, it describes in detail below. According to the study by the present inventors, in the present invention having the above-described structure, R _n in the structural formula (I) is represented by any one of the structural formulas (VI), (VII), and (VIII). It is also a desirable form.

In the compound represented by the structural formula (I), when R _n is a structure represented by any one of the structural formulas (VI), (VII) and (VIII), the structural formula (I) In other words: That is, in the order of structural formulas (VI), (VII), and (VIII), it is a case of a maleimide ring, a case of an itaconimide ring, and a case of a citraconimide ring. Examples where the compound represented by the structural formula (I) takes this form are shown as (I-1) to (I-3).

  Furthermore, in the present invention, the water solubility of the compound represented by the structural formula (I) is preferably 1% by mass or more with respect to pure water at 25 ° C. and 1 atm.

  The active energy ray-curable liquid composition in the present invention may contain water and be used as an aqueous composition. In this case, the concentration varies depending on the application and style, and cannot be generally stated. However, in general, 1% by mass or more is preferable. Moreover, without making it water-soluble, it may be emulsified and dispersed using a known dispersion technique as appropriate, and used as an emulsion. Similarly, various encapsulation techniques can be applied.

  Moreover, the active energy ray-curable liquid composition in the present invention may contain a coloring material. In that case, the liquid composition according to the present invention can be used as an ink. The configuration and the color material used in that case will be described.

  The active energy ray-curable liquid composition of the present invention can be used as a colored active energy ray-curable ink that is cured by irradiation with an active energy ray or the like when applied to an ink containing a coloring material. . As the color material used in this case, it is preferable to use a pigment dispersion in which a pigment is uniformly dispersed in an aqueous medium. As the pigment dispersion, water-based gravure inks, water-based pigment dispersions for writing instruments, pigment dispersions used in conventionally known ink-jet inks, and the like can all be suitably used. Among these, a pigment dispersion in which a pigment is stably dispersed in an aqueous medium by an anionic group is extremely suitable.

  As a pigment dispersion in which a pigment is stably dispersed in an aqueous medium by an anionic group, those described in the following publications can be used. For example, in JP-A-8-143802, JP-A-8-209048, JP-A-10-140065, US Pat. No. 5,837,045 and US Pat. No. 5,851,280. It is disclosed. In the liquid composition of the present invention, various pigment dispersions as described above can be used as the coloring material.

  Examples of the pigment used include carbon black and organic pigments. Examples of the carbon black include furnace black, lamp black, acetylene black, and channel black. Of course, conventionally well-known carbon black can be used besides these. Further, magnetic fine particles such as magnetite and ferrite, titanium black and the like may be used as the pigment.

  As the organic pigment, for example, the following can be used. Azo pigments such as Toluidine Red and Hansa Yellow. Phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green. Quinacridone pigments such as quinacridone red and quinacridone magenta. Perylene pigments such as perylene red and perylene scarlet. Isoindolinone pigments such as isoindolinone yellow and isoindolinone orange. Imidazolone pigments such as benzimidazolone yellow and benzimidazolone orange. Pilanthrone pigments such as pyranthrone red and pyranthrone orange.

  When an applicable organic pigment is indicated by a color index (CI) number, the following can be used. C. I. Pigment Yellow: 12, 13, 14, 17, 20, 24, 55, 74, 83, 86, 93, 97, 98, 109, 110, 117, 120, 125, 128, 137, 138, 139, and the like. In addition, C.I. I. Pigment Yellow: 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185 and the like. C. I. Pigment Orange: 16, 36, 43, 51, 55, 59, 61, 71, etc. C. I. Pigment Red: 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 175, 176, 177, 180, 192, 202, 209, 215, 216, 217, and the like. In addition, C.I. I. Pigment Red: 220, 223, 224, 226, 227, 228, 238, 240, 254, 255, 272, and the like. C. I. Pigment violet: 19, 23, 29, 30, 37, 40, 50, and the like. C. I. Pigment Blue: 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, and the like. C. I. Pigment Green: 7, 36, etc. C. I. Pigment Brown: 23, 25, 26, etc. Of course, in addition to these, various conventionally known organic pigments can be used.

  In addition, when using the various pigments described above, a dispersant may be used in combination. The dispersant is not particularly limited as long as it can stably disperse the pigment in the aqueous medium. For example, a block polymer, a random polymer, a graft polymer, and the like can be used. Examples include the following. Styrene-acrylic acid copolymer, styrene-maleic acid copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, or salts thereof. Examples thereof include a benzyl methacrylate-methacrylic acid copolymer or a salt thereof.

  In addition, when using the above-described various pigments, so-called self-dispersing pigments that can be dispersed in a medium without using a dispersant by bonding ionic groups to the surface of pigment particles can also be used. .

  The active energy ray-curable liquid composition of the present invention can also use various dyes as a colorant. The applicable dyes are indicated by dye color index (CI) numbers below. C. I. Acid Yellow 11, 17, 23, 25, 29, 42, 49, 61, 71, etc. C. I. Direct yellow 12, 24, 26, 44, 86, 87, 98, 100, 130, 132, 142, etc. C. I. Acid Red 1, 6, 8, 32, 35, 37, 51, 52, 80, 85, 87, 92, 94, 115, 180, 254, 256, 289, 315, 317, etc. C. I. Direct Red 1, 4, 13, 17, 23, 28, 31, 62, 79, 81, 83, 89, 227, 240, 242, 243, etc. C. I. Acid Blue 9, 22, 40, 59, 93, 102, 104, 113, 117, 120, 167, 229, 234, 254, etc. C. I. Direct Blue 6, 22, 25, 71, 78, 86, 90, 106, 199, etc. C. I. Direct black: 7, 19, 51, 154, 174, 195, etc.

  The active energy ray-curable liquid composition of the present invention can be used in the form of a “transparent ink” without containing the colorant as described above. In this case, since a color material is not contained, a substantially colorless and transparent film can be obtained. Examples of the use of such “transparent ink” include the following. For example, it is used for applications such as an undercoat for imparting various aptitudes to image recording to a recording medium, or an overcoat for the purpose of protecting the surface of an image formed with ordinary ink, and further providing decoration and gloss. be able to. In this case, the liquid composition can also contain a dispersion of colorless pigments or fine particles that are not intended for coloring, depending on applications such as oxidation prevention and fading prevention. By adding these, it is possible to improve various properties such as image quality, fastness and workability (handling property) of the recorded matter in both the undercoat and the overcoat.

  The liquid composition of the present invention may contain a reactive diluent which is a generally well-known technique. Typical examples include acryloylmorpholine, N-vinylpyrrolidone, acrylamide, methylenebisacrylamide, monosaccharide monoacrylate, oligoethylene oxide monoacrylate, and dibasic acid monoacrylate.

  The liquid composition of the present invention is intended to improve various performances and can contain various additives to the extent that the original properties are not impaired. For example, certain organic solvents are added for the purpose of imparting non-volatility to the ink, adjusting the viscosity, adjusting the surface tension, and imparting wettability to the recording medium.

  The organic solvents that can be used in the present invention are listed below. In the liquid composition of the present invention, one arbitrarily selected from these can be added. Glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, and propylene glycol monomethyl ether. Monohydric alcohols such as methanol, ethanol, propanol, butanol and pentanol.

  The active energy ray-curable liquid composition of the present invention may contain a polymerization initiator. The polymerization initiator used at this time is preferably hydrophilic in order to maximize the reactivity.

  The hydrophilic polymerization initiator used in the present invention may be any compound that generates radicals by active energy rays. In the present invention, it is preferable to use at least one compound selected from the group consisting of compounds represented by the following general formulas (A) and (C) to (F).

上記一般式（イ）中、Ｒ₂はアルキル基、又はアリール基であり、Ｒ₃は、アルキルオキシ基、フェニル基、又はＯＭであり、Ｍは、水素原子、又はアルカリ金属であり、Ｒ₄は下記一般式（ロ）で表される基である。

In the general formula (A), R ₂ is an alkyl group or an aryl group, R ₃ is an alkyloxy group, a phenyl group, or OM, M is a hydrogen atom or an alkali metal, and R ₄ Is a group represented by the following general formula (b).

上記一般式（ロ）中、Ｒ₅は、−［ＣＨ₂］_x2−（ｘ２は０乃至１）、又はフェニレン基であり、ｍ２は０乃至１０であり、ｎ２は０乃至１であり、Ｒ₆は、水素原子、スルホン酸基、カルボキシル基、ヒドロキシル基、又はこれらの塩である。

In the general formula (b), R ₅ is — [CH ₂ ] _x2 — (x2 is 0 to 1) or a phenylene group, m2 is 0 to 10, n2 is 0 to 1, ₆ is a hydrogen atom, a sulfonic acid group, a carboxyl group, a hydroxyl group, or a salt thereof.

上記一般式（ハ）中、ｍ３は１以上であり、ｎ３は０以上であり、ｍ３＋ｎ３は１乃至８である。

In the general formula (C), m3 is 1 or more, n3 is 0 or more, and m3 + n3 is 1 to 8.

上記一般式（ニ）中、Ｒ₁₀及びＲ₁₁はそれぞれ独立に、水素原子、又はアルキル基であり、ｍ４は５乃至１０である。

In the general formula (d), R ₁₀ and R ₁₁ are each independently a hydrogen atom or an alkyl group, and m4 is 5 to 10.

上記一般式（ホ）中、Ｒ₁₀及びＲ₁₁はそれぞれ独立に、水素原子、又はアルキル基であり、Ｒ₁₂は、−（ＣＨ₂）_x−（ｘは０乃至１）、−Ｏ−（ＣＨ₂）_y−（ｙは１乃至２）、又はフェニレン基であり、Ｍは水素原子、又はアルカリ金属である。

In the general formula (e), R ₁₀ and R ₁₁ are each independently a hydrogen atom or an alkyl group, and R ₁₂ is — (CH ₂ ) _x — (x is 0 to 1), —O— ( CH ₂ ) _y — (y is 1 to 2) or a phenylene group, and M is a hydrogen atom or an alkali metal.

前記一般式（ヘ）中、Ｒ₁₀及びＲ₁₁はそれぞれ独立に、水素原子、又はアルキル基であり、Ｍは水素原子、又はアルカリ金属である。

In the general formula (f), R ₁₀ and R ₁₁ are each independently a hydrogen atom or an alkyl group, and M is a hydrogen atom or an alkali metal.

  Among these, it is preferable to use the compounds represented by the general formulas (a), (c) and (d), and it is more preferable to use the compounds represented by the general formulas (a) and (c). Particularly preferred.

In addition, the alkyl group and aryl group of R ₂ in the general formula (a) may have a substituent. Examples of such substituents include the following. Halogen, an alkyl group having 1 to 5 carbon atoms, an alkyloxy group having 1 to 5 carbon atoms, a group represented by the above general formula (b), a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, a hydroxyl group or an equivalent thereof Examples include salt. As used in the present invention, R ₂ is particularly preferably an aryl group having an alkyl group having 1 to 5 carbon atoms as a substituent. Moreover, it is preferable that the counter ion which forms the salt of the sulfonic acid group, the carboxyl group, and the hydroxyl group mentioned above is as follows. For example, alkali metal, alkaline earth metal, or ammonium represented by HNR ₇ R ₈ R ₉ . In the above, R ₇ , R ₈ , and R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a monohydroxyl-substituted alkyl group having 1 to 5 carbon atoms, or a phenyl group.

Moreover, when R < ₅ > in the said general formula (b) is a phenylene group, this phenylene group may have a substituent. Examples of such substituents include the following. Examples thereof include halogen, an alkyl group having 1 to 5 carbon atoms, an alkyloxy group having 1 to 5 carbon atoms, a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, a hydroxyl group or a salt thereof. Moreover, it is preferable that the counter ion which forms the salt of an above-described sulfonic acid group, a carboxyl group, and a hydroxyl group is mentioned below. For example, alkali metal, alkaline earth metal, or ammonium represented by HNR ₇ R ₈ R ₉ . In the above, R ₇ , R ₈ , and R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a monohydroxyl-substituted alkyl group having 1 to 5 carbon atoms, or a phenyl group.

R ₆ in the general formula (b) is a hydrogen atom, a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, a hydroxyl group or a salt thereof, and the like. Moreover, it is preferable that the counter ion which forms the salt of the said sulfonic acid group, a carboxyl group, and a hydroxyl group is mentioned below. For example, alkali metal, alkaline earth metal, or ammonium represented by HNR ₇ R ₈ R ₉ . In the above, R ₇ , R ₈ , and R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a monohydroxyl-substituted alkyl group having 1 to 5 carbon atoms, or a phenyl group.

The alkyloxy group and phenyl group of R ₃ in the general formula (a) may have a substituent, and examples of the substituent include the following. For example, halogen, a C1-C5 alkyl group, and a C1-C5 alkyloxy group are mentioned. Particularly preferred R ₃ is an alkyloxy group, and among them, —OC ₂ H ₅ and —OC (CH ₃ ) ₃ .

The alkyl groups of R ₁₀ and R ₁₁ in the general formula (e) may have a substituent. Examples of such substituents include the following. For example, halogen, a sulfonic acid group or its salt, a carboxyl group or its salt, a hydroxyl group or its salt, etc. are mentioned. Moreover, it is preferable that the counter ion which forms the salt of an above-described sulfonic acid group, a carboxyl group, and a hydroxyl group is mentioned below. For example, alkali metal, alkaline earth metal, or ammonium represented by HNR ₇ R ₈ R ₉ . In the above, R ₇ , R ₈ , and R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a monohydroxyl-substituted alkyl group having 1 to 5 carbon atoms, or a phenyl group.

In general formulas (a) to (f), the alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, a methyl group, an ethyl group, or a propyl group. , Butyl group, pentyl group and the like. The alkyloxy group is preferably a linear or branched alkyloxy group having 1 to 5 carbon atoms, specifically, an alkyloxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a pentoxy group. Is mentioned. Specific examples of the alkali metal include lithium, sodium and potassium. Specific examples of the alkaline earth metal include calcium, strontium, barium and the like. Specific examples of ammonium represented by HNR ₇ R ₈ R ₉ include ammonium, dimethylethanolammonium, methyldiethanolammonium, triethanolammonium, anilinium and the like. Of course, the present invention is not limited to these.

  In the present invention, among the polymerization initiators, compounds represented by the following general formulas [b] to [d] are particularly preferable.

  In the present invention, a polymerization initiator and a sensitizer can be used in combination, or two or more kinds of polymerization initiators can be used in combination. By using a combination of two or more polymerization initiators, generation of further radicals can be expected using light having a wavelength that cannot be effectively used with one polymerization initiator. The active energy ray used in the present invention may be any as long as it can cure the liquid composition, and is preferably ultraviolet rays or electron beams. Such active energy rays can generate radicals from the polymerization initiator, but when employing an electron beam, the polymerization initiator is not necessarily used.

  The active energy ray-curable liquid composition of the present invention is effective as a liquid contained in a cartridge (liquid cartridge) having a liquid container, and as a filling liquid for the liquid cartridge. Further, the active energy ray-curable liquid composition of the present invention has an extremely excellent effect as a discharge liquid in a recording head and an ink jet recording apparatus that discharge ink by the action of thermal energy among ink jet recording methods. is there.

  Hereinafter, more specific examples and comparative examples of the active energy ray-curable liquid composition according to the present invention will be described in more detail. Of course, it goes without saying that the present invention is not limited to the following examples.

  In order to evaluate the strength, film formability, and adhesion of the film formed from the active energy ray-curable liquid composition, a pencil hardness test was performed as follows. First, after mixing each component shown in Table 1 and Table 2 and stirring sufficiently, pressure filtration is performed with a filter having a pore size of 1.2 microns, and the liquid compositions of Examples 1-12 and Comparative Examples 1-8. Was prepared. The structures of the polymerizable substances (Exemplary Compounds 1 to 3 and Comparative Compounds 1 and 2) used at that time are as shown below. The compounds represented by the general formulas [b] and [c] were used as polymerization initiators. Unless otherwise specified, the amount of a component in each liquid composition or ink means “parts by mass”. In the present invention, recording in which all of the image is filled with a pitch of 600 × 600 dpi with about 5 pl dots per pixel is referred to as 100% solid.

Using each liquid composition shown in Table 1 and Table 2, its strength and the like were evaluated as follows. Using a bar coater, the liquid compositions of Examples 1 to 12 and Comparative Examples 1 to 8 were applied to a commercially available PET (polyethylene terephthalate) film so as to be 20 g / m ² . The PET film thus obtained was irradiated with ultraviolet rays using a UV irradiation apparatus to obtain a coating film. The UV lamp used here is a UV curability evaluation apparatus model LH6B (manufactured by FUSION UV Systems Inc.), and the intensity at the irradiation position is 1,500 mW / cm ² . Moreover, the conveyance speed of PET film was 0.2 m / sec. The pencil hardness of the film thus formed was measured using a commercially available pencil hardness tester HEIDON-14D (manufactured by Shinto Chemical). The measurement results are shown in Tables 3 and 4. The pencil hardness test was performed in accordance with JIS.

  As shown in the results of Examples in Table 3 and Table 4, regardless of the non-aqueous liquid composition of Examples 1 to 6 and the aqueous liquid compositions of Examples 7 to 12, in each coating film, Pencil hardness with no practical problem was obtained. In addition, all the films | membranes formed using each liquid composition of Comparative Examples 1-8 were not fully fixed to PET film, and the pencil hardness was not able to be measured with a pencil hardness tester.

  Furthermore, the liquid composition in the ink form was evaluated. First, a cyan pigment dispersion was prepared as follows. As a pigment, C.I. I. Pigment Blue 15: 3 was used, and a random polymer of styrene / acrylic acid / ethyl acrylate (average molecular weight = 3,500, acid value = 150) was used as a dispersant. These were dispersed by a bead mill to obtain a cyan pigment dispersion having a pigment solid content of 10% by mass and a ratio of pigment (P) to binder (B) of P / B ratio = 3/1. Next, after mixing the components shown in Table 5 and stirring sufficiently, pressure filtration was performed using a filter having a pore size of 0.50 μm, and each of the cyan inks of Examples 13 to 18 and Comparative Examples 9 and 10 was applied. Prepared. The pH of the ink was adjusted with a 0.2 N aqueous sodium hydroxide solution so that the pH was finally 8.5. In Comparative Examples 9 and 10, the same Comparative Compounds 1 and 2 as used above were used. The compounds represented by the general formulas [c] and [d] were used as polymerization initiators.

The cyan inks of Examples and Comparative Examples prepared as described above were evaluated in the following manner. First, as an image forming apparatus, an on-demand type ink jet recording apparatus PIXUS550i (manufactured by Canon) that discharges ink by applying thermal energy according to a recording signal to the ink was prepared. In addition, this is modified so that active energy rays can be irradiated. Specifically, a mercury lamp is used in a portion adjacent to a recording head portion of an ink cartridge having a liquid storage portion containing the active energy ray-curable liquid composition of the present invention by using microwaves without an electrode from the outside. It was equipped with a UV lamp that excited The UV lamp used a D bulb. The intensity at the irradiation position was 1,500 mW / cm ² . Using this ink jet recording apparatus, evaluation was performed according to the evaluation methods and evaluation criteria described in (1) to (3) below.

(1) Ink curing performance (1) -1: Fixability Using the cyan inks of Examples 13 to 18 and Comparative Examples 9 and 10 and the modified inkjet recording apparatus, offset recording paper OK Kanto ( A 100% solid image was formed on (Mitsubishi Paper). A coating film (image) was obtained by irradiating ultraviolet rays in a form parallel to the recording under the same irradiation conditions as when the liquid composition was applied. Then, 10 seconds after the formation of the coating film, the Sylbon paper was placed on the recording medium, and the Sylbon paper was pulled with a load of 40 g / cm ² placed on the recording surface. The fixing property was evaluated by visually observing whether or not the non-recording portion (white background portion) and the Sylbon paper of the recording medium were stained by rubbing of the recording portion. The evaluation criteria for fixability are as follows. The evaluation results are shown in Table 6.
A: The part by rubbing is not seen.
B: Almost no dirt due to rubbing is observed.
C: Dirt due to rubbing is conspicuous.

(1) -2: Marker resistance Using the cyan inks of Examples 13 to 18 and Comparative Examples 9 and 10 and the modified inkjet recording apparatus, PPC paper (Canon) under the same conditions as described above 12 points of characters were recorded. After 1 minute of recording, the highlighter spotlight yellow (manufactured by Pilot) is used to mark (overwrite) the character part once with normal writing pressure, and visually check for the presence or absence of character disturbance. Evaluation was performed. The evaluation criteria for marker resistance are as follows. The evaluation results are shown in Table 6.
A: Character disturbance due to the marker does not occur.
B: Character disturbance due to the marker occurs slightly.
C: Character disturbance due to the marker is remarkably generated.

(2) Discharge stability Using the cyan inks of Examples 13 to 18 and Comparative Examples 9 and 10 and the modified ink jet recording apparatus, PPC paper (manufactured by Canon) under the same conditions as described above. Horizontal ruled lines were recorded continuously. Thereafter, the thickness of the ruled line and the landing position of the dots were visually observed to evaluate the ejection stability. The evaluation criteria for ejection stability are as follows. The evaluation results are shown in Table 6.
A: There is no change in the thickness of the line, and there is no shift in the landing position.
B: There is some fatness.
C: There is a thin line, and there is a slight shift in the landing position.

(3) Storage stability The cyan inks of Examples 13 to 18 and Comparative Examples 9 and 10 were placed in a Teflon (registered trademark) container and sealed. This was stored in an oven at 60 ° C. in a dark place for 1 month, and the storage stability was evaluated by comparing the average particle diameters of the pigments before and after storage. The evaluation criteria for storage stability are as follows. The evaluation results are shown in Table 6.
A: Change in average particle diameter is within ± 10% before and after storage.
B: The change of the average particle diameter is more than ± 10% and within ± 15% before and after storage.
C: Change in average particle diameter exceeds ± 15% before and after storage.

  As shown in Table 6, in each of the coating films and liquid compositions of Examples 13 to 18, excellent fixability, marker resistance, ejection stability, and storage stability were obtained. In addition, when each liquid composition of Comparative Examples 9 and 10 was used, there were some which showed a large change in the deviation of the landing position at the time of ejection and the dispersibility after storage, although partially.

  Next, a yellow pigment dispersion and a magenta pigment dispersion were prepared in the same manner as in the preparation of the cyan pigment dispersion used in Example 13, as follows.

  As a pigment, C.I. I. A yellow pigment dispersion having a pigment solid content of 10% by mass, a P / B ratio of 3/1, and an average particle diameter of 130 nm was prepared in the same manner as the preparation of the cyan pigment dispersion except that CI Pigment Yellow 13 was used. did.

  As a pigment, C.I. I. A magenta pigment dispersion having a pigment solid content of 10% by mass, a P / B ratio of 3/1, and an average particle diameter of 125 nm was prepared in the same manner as that for preparing a cyan pigment dispersion, except that CI Pigment Red 122 was used. did.

  Next, using each pigment dispersion, yellow ink and magenta ink were prepared in the same process as the cyan ink.

  In addition to the yellow ink and magenta ink obtained above, the cyan ink of Example 13 was combined to obtain an ink set of Example 19. Using this ink set, an image was recorded on offset recording paper OK Kanto (manufactured by Mitsubishi Paper Industries Co., Ltd.) using the same modified inkjet recording apparatus as that used in Example 13. Specifically, 100% solid recording of yellow and magenta, and an image (secondary color red) in which yellow and magenta were alternately printed by 50% every other pixel and consequently 100% solid recording was recorded. The yellow, magenta, and red portions of the image thus formed were evaluated for fixability by the same method and evaluation criteria as in Example 13 (respectively, Examples 19Y, 19M, and 19R). The yellow ink and magenta ink were evaluated for ejection stability and storage stability by the same method and evaluation criteria as in Example 13. The evaluation results are shown in Table 7.

  As shown in Table 7, the fixing property having no practical problem in the ink set of Example 19, and the ejection stability and the storage stability having no practical problem were obtained for Example 19Y and Example 19M. .

  As described above, according to the present invention, both the aqueous and non-aqueous forms have good curability by active energy rays and are practical even in the case of an ink form containing a coloring material. Curing performance is obtained. Furthermore, according to the present invention, it is possible to provide an ink or a liquid composition that is excellent in fixability and marker resistance of the formed image and excellent in ejection stability and storage stability. In addition, the above-described example is given for explaining the basic configuration of the present invention. For example, even when a dye is used as a coloring material, a liquid composition having the same performance as the above-described example is provided. It goes without saying that it can be done.

Claims (6)

An active energy ray-curable liquid composition comprising a compound represented by the following structural formula (I):

(In the above (I), A represents a hydrogen atom, a hydroxyl group or a monovalent organic residue which may have a substituent, and R ₁ represents a divalent organic group which may have a substituent. E represents an amide bond, R _n represents a cyclic linking group having a carbonyl group and an unsaturated carbon-carbon bond adjacent to the carbon atom of the carbonyl group, m represents a number of 0 or more, and n represents 2 (The above number is represented, and m + n = 3, and Z represents a structure having a triazine ring.) 2. The active energy ray-curable liquid composition according to claim 1, wherein A in the structural formula (I) is a structure represented by any of the following (II), (III), (IV), and (V): object.

The active energy ray-curable liquid composition according to claim 1 or 2, wherein R ₁ in the structural formula (I) is an alkylene group having 1 to 6 carbon atoms which may have a substituent. The active energy according to any one of claims 1 to 3, wherein R _n in the structural formula (I) is a structure represented by any one of the following structural formulas (VI), (VII), and (VIII). A linear curable liquid composition.

  The active energy ray according to any one of claims 1 to 4, wherein the water-solubility of the compound represented by the structural formula (I) is 1% by mass or more with respect to pure water at 25 ° C and 1 atm. A curable liquid composition.   A liquid cartridge comprising a liquid storage portion that stores any one of the active energy ray-curable liquid compositions according to any one of claims 1 to 5.