JP2009102498A - Active energy ray-curable type liquid composition and liquid cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable type liquid composition excellent in stability when it is used for a formation material of a water-soluble active energy ray-curable water-base ink or the like. <P>SOLUTION: The active energy ray-curable type liquid composition comprises a reaction substance obtained by adding a compound represented by general formula (I) to at least a condensation product of hydrolizable silane containing a cyclic ether group. <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.

  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.

  When using the oil-based ink as described above, since the organic solvent is likely to be 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 that can be applied to the composition are required.

  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, the above-mentioned compounds that are soluble in water and have two or more polymerizable functional groups in one molecule and are industrially produced are as follows. It turned out that there was such a problem. In other words, these compounds are poor in water solubility when the ethylene oxide chain is short, and conversely, when the ethylene oxide chain is long, the water solubility is obtained, but the cured film properties, in particular, the hardness, adhesion, and sticky performance are not sufficient. There is.

  Further, the compound described in Patent Document 1 described above has water solubility and can be cured by active energy rays, but the use thereof is an ink receiving layer for a recording medium. It is unknown whether it can be applied to. 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 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 a coloring material for water-based inks, generally used are dyes that are dissolved in an aqueous medium by widely used anionic groups, and pigment dispersions in which pigments are dispersed in an aqueous medium by anionic groups. On the other hand, when the water-based curable substance as described above is contained in the water-based ink, the pH of the water-based ink may be lowered to the acidic region as acrylic acid is generated by hydrolysis of the (meth) acrylic acid ester group. is there. In such a state, the original pH is adjusted to an alkali to neutral range, and the dye that originally existed stably precipitates or the pigment dispersion aggregates or settles. Problems may occur in terms of storage stability. 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.

  In response to the above problems, the present inventors have found an active energy ray-curable liquid composition comprising a compound having a plurality of non-hydrolyzable photopolymerizable groups in one molecule and exhibiting water solubility. . Various methods for solubilizing a curable substance have been proposed. However, the present invention, unlike the above method, utilizes a reaction product obtained by adding a non-hydrolyzable photopolymerizable compound having a hydroxyl group to a condensate of a hydrolyzable silane containing a cyclic ether group. Is.

  On the other hand, Japanese Patent Application Laid-Open No. 2002-188057 discloses an aqueous coating composition containing an epoxy silane which is a cyclic ether group-containing silane. This known example is used by emulsifying water-soluble aminosilane in combination, and its purpose is use as a coating material. That is, there is no mention of photocurable resin or photocurable ink, and it is unclear whether it can be applied to the problems of the present invention.

  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 has sufficient water-solubility, cures quickly and sufficiently with active energy rays, and the formed cured product has the following excellent characteristics, and is stable against heat and storage. It is providing the active energy ray hardening-type liquid composition excellent in property. A cured product formed by the active energy ray-curable liquid composition has excellent strength and adhesion, and excellent fixability and marker resistance. The second object of the present invention is to provide a liquid cartridge using the active energy ray-curable liquid composition.

（上記式（Ｉ）において、Ｒ¹は置換基を含んでいてもよい２価の有機基を表し、Ｒ²は少なくとも一方のカルボニル炭素に隣接した炭素原子が炭素−炭素二重結合を有している、置換基を有していてもよい２価の有機基を表す。） The above object is achieved by the present invention described below. That is, as a first embodiment of the present invention, at least a reaction product obtained by adding a compound represented by the following general formula (I) to a condensate of a hydrolyzable silane containing a cyclic ether group is included. An active energy ray-curable liquid composition is provided.

(In the above formula (I), R ¹ represents a divalent organic group which may contain a substituent, and R ² has at least one carbon atom adjacent to the carbonyl carbon having a carbon-carbon double bond. Represents a divalent organic group which may have a substituent.

（上記式（Ｉ）において、Ｒ¹は置換基を含んでいてもよい２価の有機基を表し、Ｒ²は少なくとも一方のカルボニル炭素に隣接した炭素原子が炭素−炭素二重結合を有している、置換基を有していてもよい２価の有機基を表す。）

（上記式（II）において、Ｒ³は環状エーテル基を含有しない非加水分解性の有機残基を表し、Ｒ⁴は加水分解性の有機残基を表し、ｎは０乃至３のいずれかを表す。） Further, the present invention provides, as a second embodiment, a condensate of (1) a hydrolyzable silane containing a cyclic ether group and (2) a hydrolyzable silane represented by the following general formula (II): There is provided an active energy ray-curable liquid composition comprising at least a reaction product obtained by adding a compound represented by the following general formula (I).

(In the above formula (I), R ¹ represents a divalent organic group which may contain a substituent, and R ² has at least one carbon atom adjacent to the carbonyl carbon having a carbon-carbon double bond. Represents a divalent organic group which may have a substituent.

(In the above formula (II), R ³ represents a non-hydrolyzable organic residue containing no cyclic ether group, R ⁴ represents a hydrolyzable organic residue, and n represents any of 0 to 3) To express.)

  The present invention also provides, as a third embodiment, a liquid cartridge comprising a liquid storage portion that stores at least one of the active energy ray-curable liquid compositions described above.

  According to the first and second aspects 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 in which the components constituting the liquid composition are 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 can be stably performed. Can be done. In addition, according to the third 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.

（上記式（Ｉ）において、Ｒ¹は置換基を含んでいてもよい２価の有機基を表す。Ｒ²は少なくとも一方のカルボニル炭素に隣接した炭素原子が炭素−炭素二重結合を有している、置換基を有していてもよい２価の有機基を表す。） 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 inventors of the present invention have taken into consideration the background art described above, and as a result, they have a non-hydrolyzable photopolymerizable group and a water-soluble reactant [A]. A liquid composition was found. One of the reactants [A] is a reactant obtained by adding a compound represented by the following general formula (I) to a hydrolyzable silane condensate containing a cyclic ether group.

(In the above formula (I), R ¹ represents a divalent organic group which may contain a substituent. R ² represents a carbon atom adjacent to at least one carbonyl carbon having a carbon-carbon double bond. Represents a divalent organic group which may have a substituent.

（上記式（II）において、Ｒ³は環状エーテル基を含有しない非加水分解性の有機残基を表し、Ｒ⁴は加水分解性の有機残基を表し、ｎは０乃至３のいずれかを表す。） Another form of the reaction product [A] is a condensate of (1) a hydrolyzable silane containing a cyclic ether group and (2) a hydrolyzable silane represented by the following general formula (II). A reaction product obtained by adding the compound represented by the general formula (I).

(In the above formula (II), R ³ represents a non-hydrolyzable organic residue containing no cyclic ether group, R ⁴ represents a hydrolyzable organic residue, and n represents any of 0 to 3) To express.)

In the present invention having the above-described configuration, it is also preferable that R ² in the general formula (I) is a structure represented by any one of the following structural formulas (III), (IV), and (V). It is a form.

In the compound represented by the general formula (I), when R ² is a structure represented by any one of the structural formulas (III), (IV) and (V), the structural formula (I ) Can be paraphrased as follows: That is, in the order of the structural formulas (III), (IV), and (V), the maleimide derivative, the itaconimide derivative, and the citraconic imide derivative.

  For the above-mentioned purpose, the present inventors have realized a remarkable effect that cannot be easily anticipated for the first time by using an active energy ray-curable liquid composition containing these reactants [A]. And the present invention has been accomplished. That is, by using the reactant [A] described above, it is possible to provide an active energy ray-curable liquid composition that achieves both photocurability and water solubility. And this liquid composition is very suitably applicable to the inkjet recording method. More specifically, the reactant [A] 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 reaction product [A] is excellent in strength and adhesion, and excellent in fixability and marker resistance. In addition, when the reaction product [A] is contained to form a liquid composition such as a water-based ink used for ink jet recording or the like, the liquid composition has, of course, the ejection characteristics. Excellent and stable against heat and storage. Furthermore, by providing a liquid cartridge provided with a liquid container containing the active energy ray-curable liquid composition, it is possible to stably obtain an image excellent in fixability and marking resistance. Become. In the present invention, the fact that the compound is water-soluble means that 1% by mass or more is dissolved in pure water at 25 ° C. and 1 atm.

上記反応例で示される通り、水酸基含有化合物の環状エーテル基への付加で新たな水酸基を生じるため、得られる反応物［Ａ］は、水溶性を有することができる。 Here, the reaction of a cyclic ether group and a hydroxyl group contained in the general formula (I) is shown below by taking a typical epoxy group as a cyclic ether group as an example.

As shown in the above reaction example, addition of a hydroxyl group-containing compound to a cyclic ether group generates a new hydroxyl group, and thus the reaction product [A] obtained can have water solubility.

  Needless to say, it is not necessary to react the cyclic ether group such as an epoxy group and the compound represented by the general formula (I) containing a hydroxyl group in a ratio of 1: 1. For example, after performing an addition reaction under conditions where the cyclic ether group remains excessively, the remaining cyclic ether group is added with water or alcohol to open a ring to form a new hydroxyl group, thereby increasing the water solubility. Can also be realized. In addition, the hydrolyzable silane containing a cyclic ether group may be reacted with a compound represented by the general formula (I) after being condensed with other hydrolyzable silane, if necessary.

  Examples of other hydrolyzable silanes include compounds represented by the general formula (II), and the required properties as photocurable inks (curability, water solubility, adhesion of cured products to recording media, scratch resistance, etc. Etc.) can be used by appropriately selecting the type of the silane. For example, a reaction product obtained by reacting a compound of general formula (I) with a condensate of a hydrolyzable silane containing an epoxy group and an aromatic silane (typically phenyltrialkoxysilane) is: , Has the following characteristics. That is, when the active energy ray-curable liquid composition containing the reaction product is in the form of an ink, the glass transition point (Tg) of the resulting cured product is increased due to the presence of phenyl groups, and the printed product is sticky. Can be reduced.

  As another example, a reaction product obtained by reacting a compound of the general formula (I) with a condensate of a hydrolyzable silane containing an epoxy group and a silane having a dialkylsiloxane structure has the following characteristics: Have. That is, when the active energy ray-curable liquid composition containing the reactant is in the form of an ink, the scratch resistance of the printed matter can be improved by the slipperiness derived from the dialkylsiloxane structure.

  Moreover, since it differs depending on the application and style, it cannot be generally stated, but the reactant [A] is preferably one that dissolves 1% by mass or more with respect to pure water at 25 ° C. and 1 atm. Further, 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.

Next, the hydrolyzable silane containing a cyclic ether group used in the present invention will be described based on specific examples. In the present invention, the hydrolyzable silane containing a cyclic ether group is a silane compound having an alkoxy group, a halogen group or the like as a hydrolyzable group. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxycyclohexylethyltrimethoxysilane,
Examples thereof include epoxy silanes such as epoxy cyclohexyl ethyl triethoxy silane and oxetane ring compounds such as 3-ethyl (triethoxysilylpropoxymethyl) oxetane. Of course, in the present invention, the hydrolyzable silane containing a cyclic ether group is not limited to the above compound.

  In the present invention, the hydrolyzable silane represented by the general formula (II), which may be used together with / condensed with the cyclic ether group-containing hydrolyzable silane, will be described. By using the silane, for example, when the liquid composition of the present invention is in the form of an ink, various functions can be imparted. For example, the fastness of the cured product obtained can be improved by using a phenyl group-containing silane. Further, by using silane or fluorosilane having a dialkylsiloxane structure, it is possible to improve the wettability to the recording medium and the scratch resistance of the cured product.

Specific examples of the hydrolyzable silane represented by the general formula (II) include the following. Alkoxysilanes such as Si (OCH ₃ ) ₄ and Si (OCH ₂ CH ₃ ) ₄ . _{C 6 H 5 Si (OCH 3} ) 3, C 6 H 5 Si (OCH 2 CH 3) 3, C 6 H 5 CH 2 Si (OCH 2 CH 3) 3, C 6 H 5 CH 2 CH 2 Si (OCH ₃ ) Aryl silanes such as ₃ and C ₆ H ₄ (CH ₂ CH ₂ Si (OCH ₃ ) ₃ ) ₂ . CH ₃ Si (OCH ₃ ) ₃ , CH ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ CH ₂ Si (OCH ₃ ) ₃ , CH ₃ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CH ₃ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
CH ₃ CH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCH ₃ ) ₂ , (CH ₃ ) ₂ Si (OCH ₂ CH ₃ ) ₂ , (CH ₃ CH ₂ ) ₂ Si (OCH ₃ ) ₂ , (CH ₃ CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₂ , CH ₃ (C ₆ H ₅ ) Si (OCH ₃ ) ₂ , CH ₃ (C ₆ H ₅ ) Si (OCH ₂ CH _{3) 2,}
Alkylsilanes such as (C ₆ H ₅ ) ₂ Si (OCH ₃ ) ₂ and (C ₆ H ₅ ) ₂ Si (OCH ₂ CH ₃ ) ₂ . _{CH 2 = CHSi (OCH 3)} 3, CH 2 = CHSi (OCH 2 CH 3) 3, CH 2 = CHC 6 H 4 Si (OCH 3) 3, CH 2 = CHC 6 H 4 Si (OCH 2 CH 3) ₃ and other vinyl silanes.
H ₂ NCH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ Si (OCH ₂ CH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Aminosilanes such as SiCH ₃ (OCH ₃ ) ₂ .
CH ₂ = CHCOOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
_{CH 2 = CHCOOCH 2 CH 2 CH} 2 Si (OCH 2 CH 3) 3, CH 3 CH = CHCOOCH 2 CH 2 CH 2 Si (OCH 3) 3,
CH ₃ CH═CHCOOCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ CH═CHCOOCH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ,
Acrylic or methacrylic silane such as _{CH 3 CH = CHCOOCH 2 CH 2} CH 2 SiCH 3 (OCH 2 CH 3) 2. CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
CF ₃ CF ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
Fluorosilane, such _{CF 3 CF 2 CF 2 CF 2} CF 2 CF 2 CH 2 CH 2 Si (OCH 2 CH 3) 3. Of course, in the present invention, the hydrolyzable silane represented by the general formula (II) is not limited to the above compound.

  In the present invention, these hydrolyzable silanes represented by the general formula (II) can be condensed with a hydrolyzable silane containing a cyclic ether group alone or in combination of a plurality of types. Further, after condensing only the hydrolyzable silane represented by the general formula (II), the hydrolyzable silane containing a cyclic ether group may be further condensed. On the other hand, when using a silane reactive with an epoxy group, such as aminosilane, as the hydrolyzable silane represented by the general formula (II), care should be taken so that gelation does not occur depending on the amount added or the timing of addition. May be necessary. In addition, when acrylic silane or methacryl silane is used, it may be necessary to consider the addition amount as appropriate within a range that does not adversely affect hydrolysis.

  The present inventors applied the active energy ray-curable liquid composition containing the reactant [A] described above to the ink jet recording method, and evaluated its ejection stability and cured film. 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. . Furthermore, it showed high performance in adhesion to the recording medium. In other words, it exhibited extremely excellent overall performance as an active energy ray-curable liquid composition.

  The reason why such excellent performance is manifested is not clear, but the present inventors presume as follows. First, although it is water-soluble, it is speculated that the reaction product [A] has a hydroxyl group and that the siloxane skeleton in the reaction product [A] has high hydrophilicity. Moreover, it is estimated that about favorable sclerosis | hardenability was expressed on the basis of the structural characteristics etc. which the reaction material [A] has as follows. First, the reactant [A] has a carbonyl group and a cyclic linking group having an unsaturated carbon-carbon bond adjacent to the carbon atom of the carbonyl group. And it is speculated that this structure has polymerizability, that it is polyfunctional, and that the crosslink density tends to increase structurally and that it becomes a dense cured film. Furthermore, regarding the stability, it is presumed that there is no or little bond mode (for example, acrylate group) that is relatively inferior in the reaction product [A]. Furthermore, regarding the adhesiveness to the recording medium, it is considered that the hydroxyl group and siloxane skeleton of the reactant [A] exhibit a good wetting property on the recording medium.

  Moreover, the active energy ray-curable liquid composition of the present invention may contain water and be used as an aqueous composition. Moreover, the active energy ray-curable liquid composition of 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 particularly preferable.

  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 known carbon black can be used in addition to 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 such as hydroxyethyl acrylamide or methylene bisacrylamide. In addition, monosaccharide monoacrylates, oligoethylene oxide monoacrylates, dibasic acid monoacrylates, and the like are also included.

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

上記一般式（イ）中、Ｒ₅はアルキル基、又はアリール基であり、Ｒ₆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、Ｒ₇は下記一般式（ロ）で表される基である。

In the general formula (A), R ₅ is an alkyl group or an aryl group, R ₆ is an alkyloxy group, a phenyl group, or OM, M is a hydrogen atom or an alkali metal, and R ₇ Is a group represented by the following general formula (b).

上記一般式（ロ）中、Ｒ₈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、Ｒ₉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 ₈ is — [CH ₂ ] _x2 — (x2 is 0 to 1) or a phenylene group, m2 is 0 to 10, n2 is 0 to 1, ₉ is a hydrogen atom, a sulfonic acid group, a carboxyl group, a hydroxyl group, or a salt thereof.

Preferable specific examples of the general formula (A) include compounds represented by the following structural formula [B].

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.

Preferable specific examples of the general formula (c) include compounds represented by the following structural formula [C].

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.

Preferable specific examples of the general formula (2) include compounds represented by the following structural formula [D].

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. Of course, the present invention is not limited to these.

  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. Further, the polymerization initiator as described above is not necessarily used when an electron beam curing method in which a liquid composition is cured using an electron beam as an active energy beam.

  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, the components shown in Table 1 were mixed and sufficiently stirred, and then pressure filtration was performed with a filter having a pore size of 1.2 microns to prepare liquid compositions of Examples 1 to 10 and Comparative Examples 1 to 4. did. Exemplified compounds 1 to 5 used at that time were prepared as follows. Moreover, the structures of the used comparative compounds 1 and 2 are as shown below, and the structures of the polymerization initiators B and C used are as shown in the structural formulas [B] and [C], respectively. 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.

[Preparation of Exemplified Compound 1]
3-glycidoxypropyltrimethoxysilane was used as a hydrolyzable silane containing a cyclic ether group, and this was condensed using ion-exchanged water to produce a silane condensate. Subsequently, the maleimide derivative represented by the structural formula (I-1) was added at a ratio of 0.7 equivalent to the epoxy group in the silane condensate, and these were subjected to addition reaction using pyridine as a catalyst. Then, exemplary compound 1 was obtained by removing pyridine, a reaction solvent, and water from the obtained reaction solution.

[Preparation of Exemplified Compound 2]
Exemplified Compound 2 was obtained in the same manner as Exemplified Compound 1 except that epoxycyclohexylethyltrimethoxysilane was used instead of 3-glycidoxypropyltrimethoxysilane.

[Preparation of Exemplified Compound 3]
Exemplified Compound 3 was obtained in the same manner as Exemplified Compound 1, except that an itacimide derivative represented by Structural Formula (I-2) was used instead of the maleimide derivative represented by Structural Formula (I-1).

[Preparation of Exemplified Compound 4]
3-glycidoxypropyltrimethoxysilane is shown as the hydrolyzable silane containing a cyclic ether group, and C ₆ H ₅ Si (OCH ₂ CH ₃ ) ₃ is shown as the hydrolyzable silane represented by the general formula (II). Phenylsilane was used. These were condensed using ion-exchanged water at a molar ratio of 3: 1 to produce a silane condensate. Next, the maleimide derivative represented by the structural formula (I-1) was added at a ratio of 0.7 equivalent to the epoxy group in the silane condensate, and these were subjected to addition reaction using pyridine as a catalyst. Then, exemplary compound 4 was obtained by removing pyridine, a reaction solvent, and water from the obtained reaction solution.

[Preparation of Exemplified Compound 5]
As the hydrolyzable silane represented by the general formula (II), an alkylsilane represented by (CH ₃ ) ₂ Si (OCH ₃ ) ₂ was used and condensed using ion-exchanged water. Subsequently, 3-glycidoxypropyltrimethoxysilane, which is a hydrolyzable silane containing a cyclic ether group, was added, and the condensation reaction was further advanced to produce an alkylsilane / epoxysilane condensate. Next, the maleimide derivative represented by the structural formula (I-1) was added at a ratio of 0.7 equivalent to the epoxy group in the silane condensate, and these were subjected to addition reaction using pyridine as a catalyst. Then, exemplary compound 5 was obtained by removing pyridine, a reaction solvent, and water from the obtained reaction solution.

Comparative compounds 1 and 2 used in the comparative examples are as follows.

Using each liquid composition shown in Table 1, its strength and the like were evaluated as follows. Using a bar coater, the liquid compositions of Examples 1 to 10 and Comparative Examples 1 to 4 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 Table 2. The pencil hardness test conforms to JIS.

  As shown in the results of the examples in Table 2, in each of the coating films formed using the liquid compositions of Examples 1 to 10, pencil hardness having no practical problem was obtained. In addition, although the film | membrane formed using each liquid composition of Comparative Examples 1-4 was hardened | cured, all were not fully fixed to PET film, but measured the pencil hardness with a pencil hardness tester. I could not.

  Subsequently, each evaluation of curability, ejection stability, and storage stability was performed on the liquid composition in the ink state containing the coloring material. 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. And these are disperse | distributed by a bead mill, The pigment solid content is 10 mass%, The mass ratio of pigment (P) and binder (B) is P / B ratio = 3: 1, The cyan pigment dispersion which is 3: 1 is obtained. It was. Next, the components shown in Table 3 including the obtained pigment dispersion were mixed and sufficiently stirred, and then pressure filtration was performed using a filter having a pore size of 0.50 μm. Examples 11 to 20 and Comparative Examples 5 to 6 cyan inks were prepared. The pH of the ink was adjusted using a 0.1 N aqueous sodium hydroxide solution so that the pH was finally 8.5. In Comparative Examples 5 to 6, the same comparative compounds 1 and 2 as used above were used.

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. The apparatus was modified so that it could be irradiated with active energy rays and used for the test. Specifically, a UV lamp that excites a mercury lamp with no electrode from the outside using a microwave is mounted on a portion adjacent to the recording head portion. The UV lamp used a D bulb, but 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 Offset recording paper OK Kanto using each of the cyan inks of Examples 11 to 20 and Comparative Examples 5 to 6 and the modified ink jet recording apparatus. A 100% solid image was formed on (Mitsubishi Paper). Under the same irradiation conditions as when the above-mentioned liquid composition was applied, ultraviolet rays were irradiated in a form parallel to the ink jet recording to obtain a coating film (image). 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. As a result, the fixing property was evaluated by visually observing whether or not the non-recording part (white background part) and the Sylbon paper of the recording medium were stained by rubbing of the recording part. The evaluation criteria for fixability are as follows. The evaluation results are shown in Table 4.
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 11 to 20 and Comparative Examples 5 to 6, and the modified ink jet recording apparatus, PPC paper ( 12 point characters were recorded on Canon). 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 the presence or absence of character disturbance is visually observed to make the marker resistant. Was evaluated. The evaluation criteria for marker resistance are as follows. The evaluation results are shown in Table 4.
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 11 to 20 and Comparative Examples 5 to 6 and the modified inkjet recording apparatus, PPC paper (manufactured by Canon) under the same conditions as described above. A horizontal ruled line was 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 4.
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 11 to 20 and Comparative Examples 5 to 6 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 4.
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 4, in each coating film (image) and liquid composition formed with the liquid compositions of Examples 11 to 20, excellent fixability, marker resistance, ejection stability, and storage stability Sex was obtained. When each of the liquid compositions of Comparative Examples 5 to 6 was used, there was a partial change in landing position at the time of ejection and a large change in dispersibility after storage.

  Next, a yellow pigment dispersion and a magenta pigment dispersion were prepared as described below in the same manner as the cyan pigment dispersion used in Example 14.

  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 size 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 the preparation of the 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 14 was combined to form an ink set of Example 14 'consisting of three colors of ink. An image was recorded on offset recording paper OK Kanto (manufactured by Mitsubishi Paper Industries) using the same ink jet recording apparatus as that used in Example 14 using the two colors of ink in this ink set. 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 formed in this way were evaluated for fixability by the same method and evaluation criteria as in Example 14 (respectively, Examples 14Y, 14M, and 14R). In addition, the yellow ink of Example 14Y and the magenta ink of Example 14M were evaluated for ejection stability and storage stability by the same method and evaluation criteria as in Example 14. The evaluation results are shown in Table 5.

  As shown in Table 5, the fixing property having no practical problem in the ink set of Example 14 ′ was obtained, and the ejection stability and the storage stability having no practical problem were obtained in Examples 14Y and 14M. It was.

  As described above, according to the present invention, practical curing performance can be obtained even when the curability by active energy rays is good and the ink form contains a coloring material. Furthermore, when used for image formation such as an inkjet recording formation method, an ink or a liquid composition excellent in image fixing property, marker resistance, ejection stability and storage stability can be provided. 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 reaction product obtained by adding a compound represented by the following general formula (I) to a condensate of a hydrolyzable silane containing a cyclic ether group: object.

(In the above formula (I), R ¹ represents a divalent organic group which may contain a substituent, and R ² has at least one carbon atom adjacent to the carbonyl carbon having a carbon-carbon double bond. Represents a divalent organic group which may have a substituent. (1) A compound represented by the following general formula (I) is added to a condensate of a hydrolyzable silane containing a cyclic ether group and (2) a hydrolyzable silane represented by the following general formula (II). An active energy ray-curable liquid composition comprising at least a reaction product comprising:

(In the above formula (I), R ¹ represents a divalent organic group which may contain a substituent, and R ² has at least one carbon atom adjacent to the carbonyl carbon having a carbon-carbon double bond. Represents a divalent organic group which may have a substituent.

(In the above formula (II), R ³ represents a non-hydrolyzable organic residue containing no cyclic ether group, R ⁴ represents a hydrolyzable organic residue, and n represents any of 0 to 3) To express.) The active energy ray-curable liquid according to claim 1 or 2, wherein R ² in the general formula (I) is a structure represented by any one of the following structural formulas (III), (IV), and (V). Composition.

  The water solubility of the reaction product obtained by adding the compound represented by the general formula (I) to the condensate of hydrolyzable silane containing a cyclic ether group is 1% by mass with respect to pure water at 25 ° C. and 1 atm. The active energy ray-curable liquid composition according to claim 1 or 3, which is dissolved as described above.   (1) A compound represented by general formula (I) is added to a condensate of hydrolyzable silane containing a cyclic ether group and (2) hydrolyzable silane represented by general formula (II). The active energy ray-curable liquid composition according to claim 2 or 3, wherein the water solubility of the reaction product is 1% by mass or more with respect to pure water at 25 ° C and 1 atm.   A liquid cartridge comprising a liquid storage unit that stores at least one of the active energy ray-curable liquid compositions according to claim 1.