JP5244354B2 - Ink jet ink composition, and ink jet recording method and printed matter using the same - Google Patents

Description

  The present invention relates to an ink-jet ink composition that is suitably used for ink-jet recording, an ink-jet recording method, and a printed matter obtained by the ink-jet recording method. Specifically, an ink composition suitable for ink jet recording, which is cured with high sensitivity to irradiation with actinic radiation and the cured product has sufficient flexibility even after ink curing, an ink jet recording method, and the same are used. It relates to printed matter.

  As an image recording method for forming an image on a recording medium such as paper based on an image data signal, an electrophotographic method, a sublimation / melting thermal transfer method, an ink jet method, and the like are known. Among these, the ink jet method can be implemented with an inexpensive apparatus, and the ink is efficiently used because it forms an image directly on a recording medium by ejecting ink only to a required image portion. The running cost is low, the noise is low, and the image recording method is excellent. According to the inkjet method, printing is possible not only on plain paper but also on non-water-absorbing recording media such as plastic sheets and metal plates, but speeding up and high image quality are important issues when printing. In addition, the time required for drying and curing the droplets after printing has a property of greatly affecting the sharpness of the image.

As one of the ink jet methods, there is a recording method using a curable ink composition for ink jet recording that can be cured by irradiation with actinic radiation. According to this method, a sharp image can be formed by irradiating with radiation immediately after printing and curing the ink droplets.
The curable ink composition is required to have high pigment dispersibility and stability over time in order to form a high-definition image having excellent color developability. Generally, in order to give a clear color tone and high coloring power to an ink composition, it is essential to make the pigment finer. In particular, in an ink composition for ink jet recording, the ejected ink droplets have a sharpness of the image. Therefore, it is essential to use particles that are smaller in volume than the thickness of the ink cured film formed by the ink composition. As described above, if the pigment is made finer to obtain a high coloring power, it becomes difficult to disperse the pigment, and a pigment aggregate is formed. When the pigment dispersant is added, the viscosity of the ink composition is increased. The problem of rising. The occurrence of pigment aggregates and the increase in the viscosity of the ink composition both adversely affect the ink ejection properties and cause a significant decrease in the performance of the ink composition. Further, the ink composition used in the ink jet method is housed in a cartridge, heated during ejection, and cooled during non-ejection and storage, and thus undergoes repeated heating-cooling temperature changes. There is a problem in that the dispersibility is adversely affected, the dispersibility of the pigment is lowered with time, and thickening and aggregation are likely to occur.

Therefore, there is a need for an ink composition that has sufficient fluidity and stably disperses a finely divided pigment, and that is excellent in the temporal stability of pigment dispersion. Various proposals have been made on dispersants for obtaining liquids.
For example, an ink composition using a pigment derivative as a dispersant (see Patent Documents 1 and 2), a specific group such as phthalocyanine or quinacridone to improve the affinity with the pigment, a basic group as a dispersant. An ink composition using a polymer having a polymer (see Patent Document 3), a dispersant such as poly (ethyleneimine) -poly (12-hydroxystearic acid) graft polymer, and a specific monomer that dissolves the dispersant; An ink composition that does not use an organic solvent (see Patent Document 4) has been proposed.
However, in the case of these ink compositions, although the pigment dispersion stability is improved by the function of the dispersant as compared with the conventional case, the fineness of the pigment used is insufficient, and the further fine pigment particles There is room for improvement in the dispersibility improvement effect, and there is a problem that the dispersion stability after a long period of time or after repeated temperature changes is not sufficient.

  In addition, there is a demand for achieving a desired color gamut, and for this purpose, radiation curable inkjet inks using special color pigments such as Pigment Orange and Pigment Green are disclosed (for example, see Patent Document 5).

JP 2003-119414 A JP 2004-18656 A JP 2003-321628 A JP 2004-131589 A Special table 2003-53223 gazette

  The problem to be solved by the present invention is to solve the above-mentioned problems and achieve the following objects. That is, the present invention is excellent in dispersibility and stability of fine pigments, excellent in color reproducibility, can form high-quality images with clear color tone and high coloring power, and is irradiated with actinic radiation. An object of the present invention is to provide a curable ink composition suitable for inkjet recording, and a high-quality image recording method and image recording material using the ink composition.

  As a result of intensive investigations by the present inventors in order to solve the above problems, when a specific graft polymer is used as a pigment dispersant, it is excellent in pigment dispersibility, and after long-term storage and repeated temperature changes. However, it has been found that an ink composition in which a decrease in dispersion stability is effectively suppressed can be obtained.

The above-mentioned problems of the present invention have been solved by the means described in <1>, <7> and <9> below. It describes below with <2>-<6> and <8> which are preferable embodiments.
<1> An inkjet ink comprising at least one organic pigment exhibiting orange, violet, or green color, a polymer compound represented by the following formula (1), and an actinic radiation curable compound: Composition,

〔式中、Ｒ¹は、（ｍ＋ｎ）価の有機連結基を表し、Ｒ²は単結合又は２価の有機連結基を表す。Ａ¹は、酸性基、塩基性窒素原子を有する基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基、及び水酸基よりなる群から選択された基を有する１価の有機基を表し、ｎ個のＡ¹は同一であっても、異なっていてもよい。ｍは１〜８、ｎは２〜９を表し、ｍ＋ｎは３〜１０を満たす。Ｐ¹は高分子骨格を表す。〕

[Wherein, R ¹ represents an (m + n) -valent organic linking group, and R ² represents a single bond or a divalent organic linking group. A ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and It represents a monovalent organic group having a group selected from the group consisting of a hydroxyl group, and n A ^{1 s} may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton. ]

<2> The inkjet ink composition according to <1>, wherein the polymer compound is represented by the following formula (2):

〔式中、Ｒ³は、（ｍ＋ｎ）価の有機連結基を表し、Ｒ⁴及びＲ⁵は、各々独立に単結合又は２価の有機連結基を表す。Ａ²は、酸性基、塩基性窒素原子を有する基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基、及び水酸基よりなる群から選択された基を有する１価の有機基を表し、ｎ個のＡ²は同一であっても、異なっていてもよい。ｍは１〜８、ｎは２〜９を表し、ｍ＋ｎは３〜１０を満たす。Ｐ²は高分子骨格を表す。〕

[Wherein R ³ represents an (m + n) -valent organic linking group, and R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. A ² is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and It represents a monovalent organic group having a group selected from the group consisting of a hydroxyl group, and n A ^{2 s} may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ² represents a polymer skeleton. ]

<3> The inkjet ink composition according to <1> or <2>, wherein the organic pigment is at least one selected from the group shown below.
C. I. Pigment orange 36, 38, 43, 71,
C. I. Pigment violet 23, 32, 37, 39, and C.I. I. Pigment Green 7, 36, 37
<4> The inkjet ink composition according to any one of <1> to <3>, wherein the organic pigment is at least one selected from the group shown below.
C. I. Pigment Orange 36
C. I. Pigment violet 23, 37 and C.I. I. Pigment Green 7
<5> The inkjet ink composition according to any one of <1> to <4>, wherein the organic pigment is a dioxane type compound represented by the following formula (A):

式（Ａ）中、Ｒ¹〜Ｒ¹⁰はそれぞれ独立に水素原子、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）又は１価の基を表す。

In formula (A), R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or a monovalent group.

<6> The dioxazine type compound is C.I. I. Pigment violet 23 or C.I. I. The inkjet ink composition according to <5>, which is CI Pigment Violet 37;
<7> (a ¹ ) A step of discharging the inkjet ink composition according to any one of <1> to <6> above on a recording medium, and (b ¹ ) the discharged inkjet Irradiating the ink composition with active radiation to cure the ink composition, and an ink jet recording method comprising:
<8> The actinic radiation is irradiated by a light emitting diode that generates ultraviolet rays having an emission peak wavelength in a range of 350 to 420 nm and a maximum illuminance on a recording medium surface of 10 to 2,000 mW / cm ^2. The inkjet recording method according to <7>, wherein
<9> A printed matter recorded by the inkjet recording method according to <7> or <8>.

  According to the present invention, the conventional problems can be solved, the problems can be solved, the dispersibility and stability of fine pigments are excellent, the color reproducibility is excellent, the clear color tone and the high coloring power. An ink composition suitable for inkjet recording applications, which can form a high-quality image having an optical property and can be cured by irradiation with actinic radiation, and a high-quality image recording method and image recording using the ink composition I was able to provide things.

  The inkjet ink composition of the present invention (in the present invention, the “inkjet ink composition” is also referred to as “ink composition” or “ink”) is (A) an organic pigment exhibiting an orange, violet, or green color. (B) a polymer compound represented by the above formula (1) (also referred to as “polymer of formula (1)”) and (C) an active radiation curable compound. Features. Further, it contains other components appropriately selected as necessary. The ink composition is curable when irradiated with active radiation (also referred to as active energy rays in the present invention).

  The actinic radiation (active energy ray) is not particularly limited as long as it can impart energy capable of generating a starting species of the curing reaction in the ink composition by irradiation, and depending on the purpose. For example, α ray, γ ray, X ray, ultraviolet ray, visible ray, electron beam and the like can be selected. In the present invention, among these, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferable from the viewpoint of curing sensitivity and device availability.

(Inkjet ink composition)
Hereinafter, the inkjet ink composition of the present invention will be described.
<(A) Organic pigment exhibiting orange, violet, or green color>
The ink composition of the present invention contains at least one organic pigment having an orange, violet, or green color (hereinafter also simply referred to as an organic pigment). The ink composition of the present invention is preferably an ink composition containing any one of organic pigments exhibiting orange, violet or green color. Here, the ink composition of the present invention containing an orange organic pigment is an orange ink composition, the ink composition of the present invention containing a violet organic pigment is a violet ink composition, and contains a green organic pigment The ink composition of the present invention is also referred to as a green ink composition.
For example, when a violet organic pigment is contained, one violet organic pigment can be used alone, or two or more organic pigments can be used in combination. Further, if necessary, a colorant (preferably an organic pigment) exhibiting another color can be used in combination with the ink composition.

The ink-jet ink composition of the present invention is preferably used as an ink set comprising a plurality of ink-jet ink compositions. In this case, the ink-jet ink composition is selected from the group consisting of an orange ink composition, a violet ink composition and a green ink composition. At least one ink composition. More preferably, the ink set includes an orange ink composition, a violet ink composition, and a green ink composition.
In addition to these, an ink set is preferably used in combination with ink compositions exhibiting each color of cyan, magenta, yellow, and black, and an ink composition exhibiting a white color is preferably used in combination as necessary. .

The organic pigment contained in the ink composition of the present invention is an organic pigment exhibiting at least one of violet, orange, and green.
Here, the organic pigment exhibiting an orange color means that the hue (a ^* , b ^* ) of the film obtained by applying the dispersion is “b ^* <2a ^* + 20 and b ^* > a ^* −20 (a ^* > 0, b ^* > 0) ”. Similarly, an organic pigment exhibiting a violet color means that the hue (a ^* , b ^* ) of a film obtained by applying the dispersion is “b ^* > − 2a ^* −20 and b ^* <0.5a ^* + 10”. Organic pigments within the range of (a ^* > 0, b ^* <0) and organic pigments exhibiting green color are those having a hue (a ^* , b ^* ) of a film obtained by applying the dispersion. It is defined as an organic pigment within the range of “b ^* <− a ^* + 20 and b ^* > − 0.25a ^* (a ^* <0)”. The hue (a ^* , b ^* ) can be measured using SPM100-II manufactured by Gretag.

Here, the pigment concentration of the organic pigment dispersion used for evaluating the hue is preferably 1 wt% or more and 30 wt% or less. The particle diameter (volume average particle diameter) of the organic pigment in the dispersion is not particularly limited, but is preferably 1 μm or less and more preferably 500 nm or less from the viewpoint of suppressing the influence of optical scattering. Preferably, it is 200 nm or less. The dispersion medium is not particularly limited as long as it is less colored or is not colored, but water, general-purpose solvents, commercially available monomers, and the like are preferable. The process for producing the dispersion is not particularly limited, and a known technique can be used. Since it is relatively simple, ball mill dispersion, bead mill dispersion, ultrasonic dispersion, or the like can be preferably used. Furthermore, it is preferable to use a commercially available surfactant or pigment dispersant as appropriate in the dispersion.
The substrate on which the dispersion is applied is preferably a white substrate. Although it will not specifically limit if it is a white base material, For example, commercially available white coated paper, white synthetic paper, etc. can be used preferably. The means for applying the dispersion is not particularly limited, but for example, bar coating is simple and can be preferably used.

From the viewpoint of obtaining a wide color reproducibility, the organic pigment exhibiting an orange color has a hue (a ^* , b ^* ) of a film obtained by applying the dispersion of “b ^* <2a ^* and b ^* > a. ^* (A ^* > 0, b ^* > 0) ”is more preferable. Similarly, from the viewpoint of obtaining a wide color reproducibility, as an organic pigment exhibiting a violet color, the hue (a ^* , b ^* ) of a film obtained by applying the dispersion is “b ^* > − 2a ^* and b”. ^* <0.5a ^* (a ^* > 0, b ^* <0) ”, and as an organic pigment exhibiting a green color, the hue of the film obtained by applying the dispersion (a ^* , B ^* ) is more preferably within the range of “b ^* <− a ^* (a ^* <0, b ^* > 0)”.
The organic pigment exhibiting one of the colors of violet, orange, and green is not particularly limited as long as it satisfies the above-described hue, and can be appropriately selected from commercially available products.

Examples of organic pigments exhibiting a violet color include C.I. I. Pigment violet 1 (rhodamine B), C.I. I. Pigment violet 2 (rhodamine 3B), C.I. I. Pigment violet 3 (methyl violet lake), C.I. I. Pigment violet 3: 1 (methyl violet lake), C.I. I. Pigment violet 3: 3 (methyl violet lake), C.I. I. Pigment Violet 5: 1 (Alizarin Maroon), C.I. I. Pigment violet 13 (ultramarine pink), C.I. I. Pigment violet 17 (naphthol AS), C.I. I. Pigment violet 23 (dioxazine violet), C.I. I. Pigment violet 25 (naphthol AS), C.I. I. Pigment violet 29 (perylene violet), C.I. I. Pigment violet 31 (violanslon violet), C.I. I. Pigment Violet 32 (Benzimidazolone Bordeaux HF3R), C.I. I. Pigment violet 36 (thioindigo), C.I. I. Pigment violet 37 (dioxazine violet), C.I. I. Pigment Violet 42 (Quinacridone Maroon B), C.I. I. Pigment Violet 50 (Naphthol AS) and the like are commercially available.
Among these, from the viewpoint of color reproducibility, light resistance, and stability of organic pigment dispersion, organic pigments exhibiting a violet color are C.I. I. Pigment violet 23, C.I. I. Pigment violet 32, C.I. I. Pigment violet 37 and C.I. I. Pigment Violet 39 is preferable, and Pigment Violet 23 and Pigment Violet 37 are particularly preferable.

Examples of organic pigments exhibiting an orange color include C.I. I. Pigment Orange 1 (Hansa Yellow 3R), C.I. I. Pigment orange 2 (orthonitro orange), C.I. I. Pigment orange 3 (β-naphthol), C.I. I. Pigment Orange 4 (Naphthol AS), C.I. I. Pigment orange 5 (β-naphthol), C.I. I. Pigment orange 13 (pyrazolone orange G), C.I. I. Pigment orange 15 (disazo orange), C.I. I. Pigment orange 16 (anisidine orange), C.I. I. Pigment Orange 17 (Persian Orange Lake), C.I. I. Pigment Orange 19 (Naphthalene Yellow Lake), C.I. I. Pigment orange 24 (naphthol orange Y), C.I. I. Pigment orange 31 (condensed azo orange), C.I. I. Pigment orange 34 (piazolone orange), C.I. I. Pigment Orange 36 (Benzimidazolone Orange HL), C.I. I. Pigment orange 38 (naphthol orange), C.I. I. Pigment orange 40 (pyranthron orange), C.I. I. Pigment orange 43 (perinone orange), C.I. I. Pigment Orange 46 (Ethyl Red Lake C), C.I. I. Pigment orange 48 (quinacridone gold), C.I. I. Pigment Orange 49 (Quinacridone Gold), C.I. I. Pigment orange 51 (pyranthrone orange), C.I. I. Pigment Orange 60 (Imidazolone Orange HGL), C.I. I. Pigment orange 61 (isoindolinone orange), C.I. I. Pigment Orange 62 (Benzimidazolone Orange H5G), C.I. I. Pigment orange 64 (benzimidazolone), C.I. I. Pigment orange 65 (azomethine orange), C.I. I. Pigment Orange 66 (Isoindori Orange), C.I. I. Pigment orange 67 (pyrazoloquinazolone orange), C.I. I. Pigment orange 68 (azomethine orange), C.I. I. Pigment orange 69 (isoindolinone orange), C.I. I. Pigment orange 71 (diketopyrrolopyrrole orange), C.I. I. Pigment orange 72 (imidazolone orange H4GL), C.I. I. Pigment orange 73 (diketopyrrolopyrrole orange), C.I. I. Pigment orange 74 (naphthol orange 2RLD), C.I. I. Pigment Orange 81 (diketopyrrolopyrrole orange) and the like are commercially available.
Among these, from the viewpoint of color reproducibility, light resistance, and stability of organic pigment dispersion, organic pigments exhibiting an orange color are C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 43, C.I. I. Pigment Orange 71, and C.I. I. Pigment Orange 36 is particularly preferable.

Examples of organic pigments exhibiting a green color include C.I. I. Pigment Green 1 (Brilliant Green Lake), C.I. I. Pigment Green 4 (Malachite Green Lake), C.I. I. Pigment green 7 (phthalocyanine green), C.I. I. Pigment Green 8 (Pigment Green B), C.I. I. Pigment green 10 (nickel azo yellow), C.I. I. Pigment Green 36 (brominated phthalocyanine green) and the like are commercially available.
Among these, from the viewpoint of color reproducibility, light resistance, and stability of organic pigment dispersion, organic pigments exhibiting a green color include C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment Green 37 is preferable, and C.I. I. Pigment Green 7 is particularly preferable.

  In particular, the organic pigment is preferably a dioxazine type compound from the viewpoint of good dispersibility in the component (B) described later (the polymer compound represented by the formula (1)). As a dioxazine type compound, the dioxazine compound represented by a following formula (A) can be illustrated.

In the formula, R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or a monovalent group. Moreover, any two or more of R ^{1 to} R ¹⁰ may be bonded to form a ring structure, and the ring structure may further have a substituent.
Examples of monovalent groups include amino groups, substituted amino groups, substituted carbonyl tombs, hydroxyl groups, substituted oxy groups, thiol groups, thioether groups, silyl groups, nitro groups, cyano groups, alkyl groups, alkenyl groups, aryl groups, Heterocyclic group, sulfo group, substituted sulfonyl group, sulfonato group, substituted sulfinyl group, phosphono group, substituted phosphono group, phosphonato group, substituted phosphonato group, etc. Also good.

Examples of the alkyl group in R ^{1 to} R ¹⁰ include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group And 2-norbornyl group.

When the alkyl group in R ^{1 to} R ¹⁰ has a substituent (that is, when it is a substituted alkyl group), the alkyl part of the substituted alkyl group includes a hydrogen atom on the alkyl group having 1 to 20 carbon atoms described above. Except for any one of them, a divalent organic residue can be mentioned, and the preferable range of the number of carbon atoms is the same as the above alkyl group.

Preferred examples when R ^{1 to} R ¹⁰ are substituted alkyl groups include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxycarbonylmethyl group, isopropoxymethyl group, Butoxymethyl, s-butoxybutyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, acetyloxymethyl, methylthiomethyl, tolylthiomethyl, pyridylmethyl, tetramethylpiperidinylmethyl, N-acetyltetramethylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonyl Methyl group,

  Carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group Sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyl Octyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxy Propyl group, phosphona Oxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2- Examples include methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, and 3-butynyl group.

Examples of the substituent that can be introduced into the alkyl group in R ^{1 to} R ¹⁰ include monovalent substituents composed of nonmetallic atoms exemplified below in addition to the substituents described in the description of the substituted alkyl group. Can be mentioned. Preferred examples including the above-described substituent include a halogen atom (—F, —Br, —Cl, —I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryl. Dithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, aryl Sulfoxy group, acylthio group, acylamino group, -Alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N '-Dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N '-Diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl A ru-N′-aryl-N-arylureido group,

Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N- di arylcarbamoyl group, N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group (sul Nato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinaimoyl group, N-arylsulfinamoyl group, N, N-diaryl Sulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N- Diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group,

A phosphono group (—PO ₃ H ₂ ) and its conjugate base group (referred to as a phosphonate group), a dialkylphosphono group (—PO ₃ (alkyl) ₂ ) “alkyl = alkyl group, hereinafter the same”, a diarylphosphono group ( -PO ₃ (aryl) ₂ ) “aryl = aryl group, hereinafter the same”, alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ (alkyl)) and its Conjugated base group (referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂₎ ) and (referred to as phosphonatooxy group), dialkylphosphono group (-OPO ₃ H (alkyl) its conjugate base group _2), diarylphosphono Alkoxy group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-OPO ₃ H (alkyl)) and its conjugated base group (Referred to as alkylphosphonatoxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy group), cyano group, nitro group, aryl group Alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

Specific examples of the alkyl moiety in the substituent that may be introduced to the alkyl group for R ¹ to R ¹⁰ are the same as when the R ¹ to R ¹⁰ described above is a substituted alkyl group, and preferred ranges are also the same.
Specific examples of the aryl moiety in the substituent that can be introduced into the alkyl group in R ^{1 to} R ¹⁰ include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, and a bromo group. Phenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylamino Phenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophene Group, a sulfophenyl group, phosphono phenyl group, phosphonium Hona preparative phenyl group, and the like.

Examples of the alkenyl group in R ^{1 to} R ¹⁰ include alkenyl groups having 2 to 20 carbon atoms. Among these, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 8 carbon atoms is more preferable. The alkenyl group may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. The halogen atom is a linear or branched chain having 1 to 10 carbon atoms. A cyclic alkyl group is preferred. Specific examples of the alkenyl group include, for example, vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, Examples include 2-methyl-1-propenyl group, 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group and the like.

Examples of the alkynyl group in R ^{1 to} R ¹⁰ include alkynyl groups having 2 to 20 carbon atoms. Among these, an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 8 carbon atoms is more preferable. Specific examples thereof include ethynyl group, 1-propynyl group, 1-butynyl group, phenylethynyl group, trimethylsilylethynyl group and the like.

Examples of the aryl group in R ^{1 to} R ¹⁰ include a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

The aryl group in R ^{1 to} R ¹⁰ may have a substituent on the carbon atom forming the ring, and as such a substituent, a monovalent substituent composed of a non-metal atom Is mentioned. Preferable examples of the substituent to be introduced include those described above in the description of the alkyl group, the substituted alkyl group, and the substituent in the substituted alkyl group.

The heterocyclic group for R ^{1 to} R ¹⁰ is preferably a 3- to 8-membered heterocyclic group, more preferably a 3- to 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom. A 5- to 6-membered heterocyclic group containing an atom, oxygen atom or sulfur atom is more preferred. Specifically, pyrrole ring group, furan ring group, thiophene ring group, benzopyrrole ring group, benzofuran ring group, benzothiophene ring group, pyrazole ring group, isoxazole ring group, isothiazole ring group, indazole ring group, benzoiso Xazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, Pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidin ring group, phenanthridine ring group, carbazole ring group, purine ring group, pyran ring group, piperidine ring group, Piperazine ring group, morpholine ring group, indole ring group, indolizine ring group, Road ring group, a cinnoline ring group, an acridine ring group, a phenothiazine ring group, a tetrazole ring group, a triazine ring group.

Moreover, the heterocyclic group in R < ¹ > -R < ¹⁰ > may have a substituent on the carbon atom which forms a ring, As such a substituent, monovalent substitution comprised from a nonmetallic atom is included. Groups. Preferable examples of the substituent to be introduced include those described above in the description of the alkyl group, the substituted alkyl group, and the substituent in the substituted alkyl group.

The silyl group in R ^{1 to} R ¹⁰ may have a substituent, is preferably a silyl group having 0 to 30 carbon atoms, more preferably a silyl group having 3 to 20 carbon atoms, and has 3 to 10 carbon atoms. More preferred is a silyl group. Specific examples thereof include a trimethylsilyl group, a triethylsilylyl group, a tripropylsilyl group, a triisopropylsilyl group, a cyclohexyldimethylsilyl group, and a dimethylvinylsilyl group.

The thiol group in R ^{1 to} R ¹⁰ may have a substituent, preferably a thiol group having 0 to 30 carbon atoms, more preferably a thiol group having 3 to 20 carbon atoms, Ten thiol groups are more preferred. Specific examples thereof include a mercaptomethyl group, a mercaptoethyl group, a 4-mercaptocyclohexyl group, and a 4-mercaptophenyl group.

The thioether group in R ^{1 to} R ¹⁰ may have a substituent, preferably a thioether group having 0 to 30 carbon atoms, more preferably a thioether group having 3 to 20 carbon atoms, Ten thioether groups are more preferred.
Specific examples thereof include alkylthio groups such as methylthio group, ethylthio group and cyclohexylthio group, arylthio groups such as phenylthio group, and the like.
As a halogen atom in R < ¹ > -R < ¹⁰ >, a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom are mentioned, Among these, a chlorine atom and a bromine atom are preferable.

As the substituted oxy group (R ⁰⁶ O—) in R ^{1 to} R ¹⁰ , those in which R ⁰⁶ is a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom can be used. Preferred substituted oxy groups include alkoxy, aryloxy, acyloxy, carbamoyloxy, N-alkylcarbamoyloxy, N-arylcarbamoyloxy, N, N-dialkylcarbamoyloxy, N, N-diarylcarbamoyloxy. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups described above. Examples of the acyl group (R ⁰⁷ CO—) in the acyloxy group include those in which R ⁰⁷ is the alkyl group, substituted alkyl group, aryl group, and substituted aryl group mentioned above. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyl Alkoxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, phosphonatoxy group, and the like.

The amino group in R ^{1 to} R ¹⁰ may be a substituted amino group including an amide group. The substituted amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) including an amide group is a group in which R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are monovalent nonmetallic atomic groups excluding hydrogen atoms Can be used. R ⁰⁹ and R ⁰¹⁰ may combine to form a ring. Preferred examples of the substituted amino group include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, an acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N′-alkyl-N′-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, '-Dialkyl-N'-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkylureido group, N ', N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxy A carbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, and an N-aryl-N-aryloxycarbonylamino group. Can be mentioned. Examples of the alkyl group and aryl group include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group, such as acylamino group, N-alkylacylamino group, and N-arylacylamino. R ⁰⁷ groups definitive acyl group (R ⁰⁷ CO-) are as described above. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

As the substituted sulfonyl group (R ⁰¹¹ —SO ₂ —) in R ^{1 to} R ¹⁰ , those in which R ⁰¹¹ is a group consisting of a monovalent nonmetallic atomic group can be used. More preferable examples include an alkylsulfonyl group, an arylsulfonyl group, and a substituted or unsubstituted sulfamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Specific examples of such a substituted sulfonyl group include butylsulfonyl group, phenylsulfonyl group, chlorophenylsulfonyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfuryl group. Examples include a famoyl group and an N-alkyl-N-arylsulfamoyl group.

As described above, the sulfonate group (—SO ₃ —) in R ^{1 to} R ¹⁰ means a conjugate base anion group of a sulfo group (—SO ₃ H), and is usually preferably used together with a counter cation. Such counter cations include those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.) and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^2+, etc.).

As the substituted carbonyl group (R ⁰¹³ —CO—) in R ^{1 to} R ^{10, a} group in which R ⁰¹³ is a monovalent nonmetallic atomic group can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group may be mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, more preferred substituted carbonyl groups include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, N-ary. A rucarbamoyl group can be mentioned, and even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N -Methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like.

As the substituted sulfinyl group (R ⁰¹⁴ —SO—) in R ^{1 to} R ^{10, a} group in which R ⁰¹⁴ is a monovalent nonmetallic atomic group can be used. Preferable examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl. Group, N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

The substituted phosphono group in R ^{1 to} R ¹⁰ means one in which one or two hydroxyl groups on the phosphono group are substituted by another organic oxo group. Preferred examples include the above-mentioned dialkylphosphono group, diarylphospho group. Group, an alkylarylphosphono group, a monoalkylphosphono group, and a monoarylphosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, and the like.

R ¹ to R ¹⁰ in the phosphonato group _{(-PO 3 H 2 -, -} PO 3 H-) and is derived from the phosphono group (-PO ₃ H _2), first dissociation or acid, to the second dissociation acid conjugate It means a basic anionic group. Usually, it is preferable to use it with a counter cation. Such counter cations include those generally known, that is, various oniums (ammonium, sulfonium, phosphonium, iodonium, azinium, etc.) and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ etc.).

The substituted phosphonato group in R ^{1 to} R ¹⁰ is a conjugated base anion group obtained by substituting one organic hydroxyl group with an organic oxo group among the above-mentioned substituted phosphono groups. Specific examples thereof include the above monoalkylphosphono groups. _{(-PO 3 H (alkyl))} , conjugate base of monoarylphosphono group (-PO ₃ H (aryl)) and the like.

R ^{1 to} R ¹⁰ may be bonded to each other to form a condensed ring such as a benzene ring or a heterocyclic ring together with the carbon atom to which they are bonded. Preferably, two adjacent groups of R ^{1 to} R ¹⁰ form a condensed ring, and more preferably two adjacent groups of R ^{1 to} R ⁴ and R ^{7 to} R ¹⁰ form a condensed ring. preferable.

Preferred embodiments of R ^{1 to} R ¹⁰ are listed below.
In the formula, R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom (chlorine atom, bromine atom) or a monovalent group. Moreover, any two or more of R ^{1 to} R ¹⁰ may be bonded to form a ring structure, and the ring structure may further have a substituent.
Examples of monovalent groups include amino groups, substituted amino groups, substituted carbonyl tombs, hydroxyl groups, substituted oxy groups, thiol groups, thioether groups, silyl groups, nitro groups, cyano groups, alkyl groups, alkenyl groups, aryl groups, Examples include a heterocyclic group, a substituted sulfonyl group, a sulfonate group, a substituted sulfinyl group, a substituted phosphono group, a phosphonate group, and a substituted phosphonate group.

Examples of the alkyl group in R ^{1 to} R ¹⁰ include linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms. Among these, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group. , Isohexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group.

When the alkyl group in R ^{1 to} R ¹⁰ has a substituent (that is, when it is a substituted alkyl group), the alkyl part of the substituted alkyl group includes a hydrogen atom on the alkyl group having 1 to 10 carbon atoms described above. Except for any one of them, a divalent organic residue can be mentioned, and the preferable range of the number of carbon atoms is the same as the above alkyl group.
Preferable specific examples in the case where R ^{1 to} R ¹⁰ are substituted alkyl groups include a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxycarbonylmethyl group, a butoxymethyl group, and an s-butoxybutyl group. , Methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, benzoyloxymethyl group, Acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, N-methylcarbamoylethyl group, , N-dipropylcarbamoylmethyl group, sulfonatobutyl group, N-ethylsulfamoylmethyl group, diethylphosphonobutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p -A methylbenzyl group, an allyl group, 2-butenyl group, 2-methylallyl group, 2-propynyl group, 3-butynyl group, etc. can be mentioned.

Preferable alkenyl groups in R ^{1 to} R ¹⁰ include alkenyl groups having 2 to 8 carbon atoms. The alkenyl group may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. The halogen atom is a linear or branched chain having 1 to 6 carbon atoms. A cyclic alkyl group is preferred. Specific examples of the alkenyl group include, for example, a vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-methyl-1-propenyl group, and 2-methyl-1-propenyl group. , 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group and the like.

Preferable alkynyl groups for R ^{1 to} R ¹⁰ include alkynyl groups having 2 to 8 carbon atoms. Specific examples thereof include ethynyl group, 1-propynyl group, 1-butynyl group and the like.

Preferable aryl groups in R ^{1 to} R ¹⁰ are more preferably a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, and a naphthyl group as specific examples.

The heterocyclic group for R ^{1 to} R ¹⁰ is preferably a 5- to 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom. Specifically, pyrrole ring group, furan ring group, thiophene ring group, benzopyrrole ring group, benzofuran ring group, benzothiophene ring group, isoxazole ring group, isothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring Group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, quinoline ring group, pyrimidine ring group, quinazoline ring group, quinoxaline ring group, carbazole ring group, piperidine ring group, piperazine ring group, morpholine ring group, indole Examples thereof include a ring group, an indolizine ring group, a tetrazole ring group, and a triazine ring group. A pyrrole ring group, a benzopyrrole ring group, a carbazole ring group, and an indole ring group are more preferable.

The silyl group in R ^{1 to} R ¹⁰ may have a substituent, and a silyl group having 3 to 10 carbon atoms is preferable. Specific examples thereof include a trimethylsilyl group, a triethylsilylyl group, and a tripropylsilyl group.

The thiol group in R ¹ to R ^10, which may have a substituent, preferably a thiol group of 1 to 10 carbon atoms. Specific examples thereof include a mercaptomethyl group, a mercaptoethyl group, a 4-mercaptocyclohexyl group, and a 4-mercaptophenyl group.

The thioether group in R ^{1 to} R ¹⁰ may have a substituent, and a thioether group having 1 to 10 carbon atoms is preferable. Specific examples thereof include alkylthio groups such as methylthio group, ethylthio group and cyclohexylthio group, arylthio groups such as phenylthio group, and the like.

As a halogen atom in R < ¹ > -R < ¹⁰ >, a chlorine atom and a bromine atom are preferable.

Specific examples of preferred substituted oxy groups for R ^{1 to} R ¹⁰ include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, benzyloxy group, allyloxy group, phenethyloxy group. Group, methoxyethoxy group, phenoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, methoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group and the like.

The amino group in R ^{1 to} R ¹⁰ may be a substituted amino group including an amide group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

Preferred examples of the substituted sulfonyl group for R ^{1 to} R ¹⁰ include an alkylsulfonyl group and an arylsulfonyl group. Specific examples of such a substituted sulfonyl group include a methylsulfonyl group, a butylsulfonyl group, a phenylsulfonyl group, and a chlorophenylsulfonyl group.

Preferred substituted carbonyl groups for R ^{1 to} R ¹⁰ include a formyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Specific examples include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group and the like.

Preferred substituted sulfinyl groups for R ^{1 to} R ¹⁰ include alkylsulfinyl groups and arylsulfinyl groups. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

Preferred substituted phosphono groups for R ^{1 to} R ¹⁰ include a dialkylphosphono group, a diarylphosphono group, an alkylarylphosphono group, a monoalkylphosphono group, and a monoarylphosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, and the like.

  The organic pigment represented by the formula (A) is preferably an organic pigment exhibiting a violet color. Although the organic pigment which exhibits the violet color represented by Formula (A) is illustrated below, this invention is not limited to this.

For the dispersion of the organic pigment, for example, ball mill, sand mill, attritor, roll mill, jet mill, homogenizer, paint shaker, kneader, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, etc. The apparatus can be preferably used.
In the present invention, it is particularly preferable to add the component (B) when the organic pigment is dispersed.
In addition, when dispersing the organic pigment, a synergist corresponding to various pigments may be added as a dispersion aid, if necessary. The content of the dispersion aid in the ink composition is 1 part by weight or more and 50 parts by weight or less (in the present invention, “1 part by weight or more and 50 parts by weight or less”) with respect to 100 parts by weight of the organic pigment. “50 parts by weight” or “1 part by weight to 50 parts by weight” is also preferable.

The dispersion medium used when the organic pigment is dispersed in the ink composition is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an active radiation curable compound having a low molecular weight is used as the dispersion medium. Alternatively, a solvent may be used as a dispersion medium. However, the ink composition of the present invention is a radiation curable ink composition, and preferably contains no solvent and is solvent-free in order to cure the ink composition after it is applied onto a recording medium. This is because if the solvent remains in the cured ink image, the solvent resistance is deteriorated or a VOC (Volatile Organic Compound) problem of the remaining solvent occurs. Therefore, it is preferable to use an actinic radiation curable compound as the dispersion medium, and to select a polymerizable compound having the lowest viscosity among them in terms of dispersion suitability and handling property of the ink composition.
That is, in the present invention, the component (A) (at least one of organic pigments exhibiting orange, violet, or green color) is used as a dispersant, and the component (B) (polymer compound represented by the formula (1)) is used. It is preferable to use and disperse in an actinic radiation curable compound to obtain an organic pigment dispersion.

There is no restriction | limiting in particular as an average particle diameter of an organic pigment, Although it can select suitably according to the objective, Since it is excellent in color-forming property, so that it is fine, about 0.01-0.4 micrometer is preferable, and 0.02- 0.2 μm is more preferable. Further, the maximum particle size of the organic pigment is preferably 3 μm or less, and more preferably 1 μm or less. The particle size of the organic pigment can be adjusted by selecting the organic pigment, dispersant, dispersion medium, dispersion conditions, filtration conditions, etc., and controlling the particle size of the organic pigment prevents clogging of the head nozzle. In addition, the storage stability of the ink composition, the transparency of the ink composition, and the curing sensitivity can be maintained.
In the present invention, since the component (B) having excellent dispersibility and stability is included, even when a fine organic pigment is used, a uniform and stable ink composition can be obtained. In addition, even when an organic pigment, which is a dioxazine-type compound, for which sufficient dispersibility was not obtained with conventional dispersants, an excellent ink composition with excellent color reproducibility can be obtained. You can get things.
The particle diameter of the organic pigment in the ink composition can be measured by a known measurement method. Specifically, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, a laser diffraction / scattering method, and a dynamic light scattering method.

  The content of the organic pigment in the ink composition is preferably 1 to 20% by weight, and more preferably 2 to 10% by weight.

<(B) Polymer Compound Represented by Formula (1)>
The inkjet ink composition of the present invention contains a polymer compound (also referred to as component (B)) represented by formula (1).
In the present invention, the component (B) acts or functions as a pigment dispersant, has high affinity with the component (A), has good adsorptivity to the component (A), and has a specific property. Since it is a polymer compound having a repeating structural unit, the ink composition of the present invention containing the component (B) is excellent in dispersion stability due to the steric repulsion effect of the polymer chain. The component (B) exhibits good dispersibility even when used in an organic pigment which is a dioxazine type compound that has been difficult to stably disperse in the past.

  The polymer compound represented by the following formula (1) is an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a group having 4 or more carbon atoms at the end of the polymer. Since it has a plurality of functional groups selected from the group consisting of hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups, it has excellent adsorptivity to solid surfaces, excellent micelle formation ability, and surface activity Etc. have various features. For example, it can be suitably used as a pigment dispersant.

In the formula (1), A ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, A monovalent organic group having a group selected from the group consisting of an epoxy group, an isocyanate group, and a hydroxyl group. The n A ^{1 s} may be the same or different.
Specifically, A ¹ is not particularly limited, and examples of the “monovalent organic group having an acidic group” include a carboxy group, a sulfonic acid group (—SO ₃ H), and a monosulfate ester residue. And monovalent organic groups having a group, a phosphate group, a monophosphate ester residue, a boric acid group, and the like. Among these, a carboxy group, a sulfonic acid group, a monosulfate ester residue, a phosphate group, and a monophosphate ester residue are more preferable, and a carboxy group, a sulfonic acid group, and a phosphate group are more preferable.

Examples of the “monovalent organic group having a group having a basic nitrogen atom” include, for example, a monovalent organic group having an amino group (—NH ₂ ), a substituted amino group (—NHR ⁸ , —NR ⁹ R ^10). Wherein R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl having 7 or more carbon atoms. A monovalent organic group having a guanidyl group represented by the following formula (a1), a monovalent organic group having an amidinyl group represented by the following formula (a2), and the like.

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted amino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ , and R ¹⁰ are each independently a group having 1 to 10 carbon atoms. An alkyl group, a phenyl group, and a benzyl group), a guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms; Represents a phenyl group or a benzyl group. Amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. And the like, and an amino group (—NH ₂ ), a substituted amino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently a group having 1 to 5 carbon atoms. And a guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl having 1 to 5 carbon atoms. Represents a group, a phenyl group or a benzyl group. ], In amidinyl group represented by the formula (a2) [Formula (a2), each independently R ¹³ and R ¹⁴ represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, a benzyl group. ] Is particularly preferable.

Examples of the “monovalent organic group having a urea group” include, for example, —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom or a carbon number of 1 -20 alkyl groups, aryl groups having 6 or more carbon atoms, or aralkyl groups having 7 or more carbon atoms are preferred. Among these, —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or 7 or more carbon atoms). -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms). .) Is more preferred.

Examples of the “monovalent organic group having a urethane group” include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (where R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms. Among these, —NHCOOR ¹⁸ , —OCONHR ²¹ (wherein R ¹⁸ and R ²¹ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl having 7 or more carbon atoms). -NHCOOR ¹⁸ , -OCONHR ²¹ (wherein R ¹⁸ and R ²¹ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or a carbon number). And more preferably 7 or more aralkyl groups).

Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether residue.
Preferred examples of the “hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms. Among these, a C4-C20 alkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, etc. are preferable, and a C4-C15 alkyl group (for example, an octyl group, a dodecyl group, etc.). An aryl group having 6 to 15 carbon atoms (for example, a phenyl group or a naphthyl group), an aralkyl group having 7 to 15 carbon atoms (for example, a benzyl group), or the like is more preferable.

Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.
Examples of the “epoxy group” include a group having a glycidyl group.
Examples of the “isocyanate group” include a 3-isocyanatopropyl group.
Examples of the “group having a hydroxyl group” include a 3-hydroxypropyl group.

In the above, A ¹ is a monovalent organic group having a group selected from the group consisting of an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms. Preferably there is.

The A ¹ is preferably a monovalent organic group represented by the following formula (4).

In the formula (4), B ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, R ²⁴ represents a group selected from the group consisting of an epoxy group, an isocyanate group, and a hydroxyl group, and R ²⁴ represents a single bond or an (a + 1) -valent organic linking group. a represents an integer of 1 to 10, preferably 1 to 7, more preferably 1 to 5, and particularly preferably 1 to 3. The a B ¹ may be the same or different.

B ¹ has the same meaning as A ¹ in formula (4), and the preferred embodiment is also the same.
R ²⁴ represents a single bond or an (a + 1) -valent organic linking group, and a represents 1 to 10. (A + 1) valent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, And a group consisting of 0 to 20 sulfur atoms, which may be unsubstituted or further substituted.

  Specific examples of the (a + 1) -valent organic linking group include the following structural units or groups configured by combining the structural units.

  Among the above, when the (a + 1) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

In the formula (1), R ¹ represents an (m + n) -valent organic linking group. m + n satisfies 3-10.
Examples of the (m + n) -valent organic linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups consisting of up to 200 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

  Specific examples of the (m + n) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure). .

  Examples of the (m + n) -valent organic linking group include groups composed of 1 to 60 carbon atoms, 10 or less nitrogen atoms, 40 or less oxygen atoms, 1 to 120 hydrogen atoms, and 10 or less sulfur atoms. Preferably, a group composed of 1 to 50 carbon atoms, 10 or less nitrogen atoms, 30 or less oxygen atoms, 1 to 100 hydrogen atoms, and 7 or less sulfur atoms is more preferable, and 1 to 40 carbon atoms, A group composed of 8 or less nitrogen atoms, 20 or less oxygen atoms, 1 to 80 hydrogen atoms, and 5 or less sulfur atoms is particularly preferred.

  Among the above, when the polyvalent organic linking group has a substituent, examples of the substituent include carbon such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

Among these, preferred specific examples [specific examples (1) to (17)] of the organic linking group represented by R ¹ are shown below. However, the present invention is not limited to these.

  Among the above, from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents, particularly preferred organic linking groups are the following groups.

R ² represents a single bond or a divalent organic linking group. The n R ^{2 s} may be the same or different.
The divalent organic linking group is a group composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. And may be unsubstituted or may further have a substituent.

  Specific examples of the divalent organic linking group include the following structural units or groups formed by combining the structural units.

The R ² is a single bond or a divalent composed of 1 to 50 carbon atoms, 8 or less nitrogen atoms, 25 or less oxygen atoms, 1 to 100 hydrogen atoms, and 10 or less sulfur atoms. An organic linking group is preferred and is a single bond or a divalent composed of 1 to 30 carbon atoms, 6 or less nitrogen atoms, 15 or less oxygen atoms, 1 to 50 hydrogen atoms, and 7 or less sulfur atoms. An organic linking group is more preferable, and is a single bond or a divalent group composed of 1 to 10 carbon atoms, 5 or less nitrogen atoms, 10 or less oxygen atoms, 1 to 30 hydrogen atoms, and 5 or less sulfur atoms. The organic linking group is particularly preferred.

  Among the above, when the divalent organic linking group has a substituent, examples of the substituent include carbon having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a carbon such as a phenyl group and a naphthyl group. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

In said formula (1), m represents 1-8. As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.
N represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In the formula (1), P ¹ represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. The m P ^{1 s} may be the same or different.
Among polymers, in order to constitute a polymer skeleton, a vinyl monomer polymer or copolymer, ester polymer, ether polymer, urethane polymer, amide polymer, epoxy polymer, silicone polymer, and these Modified product or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be included). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.
Furthermore, the polymer is preferably soluble in an organic solvent. A high affinity with an organic solvent is preferable because when used as a pigment dispersion medium, the affinity with the dispersion medium is high and sufficient adsorbability can be secured stably.

  Examples of the vinyl monomer include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, styrenes, and vinyl ethers. , Vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acidic group, and the like.

  Examples of the (meth) acrylate esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, (meth ) 2-hydroxyethyl acrylate, (meth) acrylic acid-2-hydroxypropiate , (Meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 2- (2-methoxyethoxy) ethyl, (meth) acrylic acid 3-phenoxy-2-hydroxypropyl, (meth) acrylic acid-2-chloroethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid-3,4-epoxy Cyclohexylmethyl, vinyl (meth) acrylate, (meth) acrylic acid-2-phenylvinyl, (meth) acrylic acid-1-propenyl, allyl (meth) acrylate, (meth) acrylic acid-2-allyloxyethyl, (Meth) acrylic acid propargyl, (meth) acrylic acid benzyl, (meth) acrylic acid diethylene glycol (Meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meta ) Polyethylene glycol monoethyl ether acrylate, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopenta (meth) acrylate Alkenyl, (meth) acrylic acid tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, (meth) acrylic acid -γ- butyrolactone, and the like.

Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of the vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate.
Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide , - methylol acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, N- allyl (meth) acrylamide, and the like.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples thereof include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc), methyl vinylbenzoate, α-methylstyrene, and the like.

Examples of the vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
Examples of the vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of the olefins include ethylene, propylene, isobutylene, butadiene, and isoprene.
Examples of the maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

  Examples of the vinyl monomer include those described above, (meth) acrylonitrile, heterocyclic groups substituted with a vinyl group (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N- Vinylacetamide, N-vinylimidazole, vinylcaprolactone, and the like can also be used. Further, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group It can be appropriately synthesized by an addition reaction between the containing monomer and monoisocyanate.

Examples of the vinyl monomer having an acidic group include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, a vinyl monomer having a phosphoric acid group, a vinyl monomer having a phenolic hydroxyl group, and a sulfonamide group. Vinyl monomers to be used.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. It is done. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid.
Examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester), phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester), and the like.

  In the present invention, among the polymers represented by the formula (1), the polymer represented by the following formula (2) is preferable.

In the formula (2), A ² has the same meaning as A ¹ in the formula (1), and the preferred embodiment is also the same.
In the formula (2), R ³ represents an (m + n) -valent organic linking group.
The (m + n) -valent organic linking group represented by R ³ has the same meaning as R ¹ in formula (1), and the preferred embodiment thereof is also the same. Specific examples include structural units similar to those described above or groups formed by combining the structural units.

In the formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. n R ^{4 s} and m R ^{5 s} may be the same or different independently.
The “divalent organic linking group” represented by R ⁴ and R ⁵ may be unsubstituted or substituted, and may be a linear, branched, or cyclic alkylene group, arylene group, aralkylene group. and, -O -, - S -, - C (= O) -, - N (R 19) -, - SO -, - SO 2 -, - CO 2 -, - N (R 20) SO 2 - Or a divalent group in which two or more of these groups are combined may be mentioned as a preferred example (the above R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). .)

Examples of R ⁴ include linear and branched alkylene groups, aralkylene groups, and —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO ₂ —, — N (R ²⁰ ) SO ₂ — (wherein R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a divalent group obtained by combining two or more of these groups Are more preferable, a linear or branched alkylene group, an aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) — (wherein R ¹⁹ represents a hydrogen atom or a carbon number of 1 to 4). Represents an alkyl group), —CO ₂ — or a divalent group in which two or more of these groups are combined is particularly preferred.

Examples of R ⁵ include a single bond or a linear or branched alkylene group, an aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO _2. —, —N (R ²⁰ ) SO ₂ — (wherein R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a combination of two or more of these groups And a linear or branched alkylene group, an aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) — (wherein R ¹⁹ represents a hydrogen atom or a carbon number). Represents 1 to 4 alkyl groups), —CO ₂ — or a divalent group in which two or more of these groups are combined is particularly preferable.

When R ⁴ and R ⁵ have a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon number of 6 such as a phenyl group and a naphthyl group. From 1 to 16 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups and the like, acyloxy groups having 1 to 6 carbon atoms, methoxy groups, ethoxy groups and the like. Carbonate esters such as alkoxy groups of up to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups of 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano groups and t-butyl carbonate Group, and the like.

In said formula (2), m represents 1-8. As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.
N represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

Further, P ² in the formula (2) represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. The preferred embodiment of the polymer, has the same meaning as P ¹ in formula (1), the same applies to its preferred embodiment.

Among the polymer compounds represented by the formula (2), in particular, R ³ is the specific example (1), (2), (10), (11), (16), or (17). R ⁴ is a single bond or a linear or branched alkylene group, an aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) — (wherein R ¹⁹ represents a hydrogen atom or Represents a C 1-4 alkyl group), —CO ₂ — or a divalent organic group obtained by combining two or more of these groups, wherein R ⁵ is a single bond, an ethylene group, a propylene group, or The following group (a) or (b), wherein P ² is a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, or a modified product thereof, and m is 1 to 1 The polymer compound having 2 and n of 3 to 6 is most preferable. In the following groups, R ²¹ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

In the present invention, the molecular weight of the polymer compound is preferably 3000 to 100,000, more preferably 5000 to 80000, and particularly preferably 7000 to 60000 in terms of weight average molecular weight. When the weight average molecular weight is within the above range, the effects of the multiple functional groups introduced at the polymer ends are fully exhibited, and the performance of adsorbing to the solid surface, micelle forming ability, and surface activity is excellent. To do. In particular, when a polymer compound is used as a pigment dispersant, good dispersibility and dispersion stability can be achieved.
The polymer compound represented by the formula (1) (including the polymer compound represented by the formula (2)) is not particularly limited, but can be synthesized by the following method. Of the following synthesis methods, the following synthesis methods such as 2, 3, 4, 5 and the like are more preferable, and the following synthesis methods such as 3, 4, 5, and the like are particularly preferable because of ease of synthesis.
1. A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group and the like is introduced at the terminal, an acid halide having a plurality of functional groups (A ¹ or A ² in the above formula), or a plurality of functional groups (the above-mentioned A method in which an alkyl halide having A ¹ or A ² in the formula, or an isocyanate having a plurality of functional groups (A ¹ or A ² in the formula) is polymerized.
2. A method in which a polymer having a carbon-carbon double bond introduced at the terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above formula) are subjected to a Michael addition reaction.
3. A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above formula) are reacted in the presence of a radical generator.
4). A method in which a polymer in which a plurality of mercaptans are introduced at a terminal and a functional group in which a carbon-carbon double bond is introduced (A ¹ or A ² in the above formula) are reacted in the presence of a radical generator.
5. A method of radical polymerization of a vinyl monomer using a mercaptan compound having a plurality of functional groups (A ¹ or A ² in the above formula) as a chain transfer agent.

  Among the above, the polymer compound of the present invention (particularly the polymer compound represented by the formula (2)) can be synthesized, for example, by any of the above methods 2, 3, 4, and 5. From the above ease, it is most preferable to synthesize by the above method 5.

  More specifically, it is preferable to perform radical polymerization using a compound represented by the following formula (3) as a chain transfer agent.

In the formula (3), R ⁶ , R ⁷ , A ³ , m, and n have the same meanings as R ³ , R ⁴ , A ² , m, and n in the formula (2), respectively. Is the same.

  Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides , Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. Examples of such include the following compounds.

  Examples of the (meth) acrylate esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate , 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) Acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether , Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, disi (meth) acrylate Clopentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromo (meth) acrylate Examples thereof include phenyl and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples thereof include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

In addition to the above compounds, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole Vinyl caprolactone can also be used.
In addition to the above compounds, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

The above vinyl monomers may be polymerized by only one kind, or may be copolymerized by using two or more kinds together. Such a radical polymer is prepared by a known method in accordance with a conventional method for each corresponding vinyl monomer. It is obtained by polymerizing.
For example, a method (solution polymerization method) in which these vinyl monomers and a chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in a solution at about 50 ° C. to 220 ° C. It is obtained by using.

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl par Peroxides such as oxides, and persulfates such as potassium persulfate and ammonium persulfate can be used.

The compound represented by the formula (3) can be synthesized by the following method or the like, but the following method 7 is more preferable because of ease of synthesis.
6). A method of converting a halide compound having a plurality of functional groups (A ¹ or A ² in the above formula) into a mercaptan compound (a method of reacting with thiourea and hydrolyzing, a method of reacting directly with NaSH, a reaction with CH ₃ COSNa And a method of hydrolyzing them).
7. Addition reaction between a compound having 3 to 10 mercapto groups in one molecule and a compound having a functional group (A ¹ or A ² in the above formula) and a functional group capable of reacting with a mercapto group How to make.

Suitable examples of the “functional group capable of reacting with a mercapto group” in Method 7 include acid halides, alkyl halides, isocyanates, and carbon-carbon double bonds.
It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is synthesized by a radical addition reaction. The carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group in terms of reactivity with the mercapto group.

  Specific examples of the "compound having 3 to 10 mercapto groups in one molecule" [specific examples (18) to (34)] include the following compounds.

  Among the above, the following compounds are particularly preferable from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

A functional group (A ¹ or A ² in the above formula) and carbon - The compound having a carbon double bond is not particularly limited, include the following.

  For example, “the compound having 3 to 10 mercapto groups in one molecule” and the above “the acid group, the group having a basic nitrogen atom, the urea group, the urethane group, the group having a coordinating oxygen atom, carbon A compound having at least one functional group selected from the group consisting of a hydrocarbon group of 4 or more, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and having a carbon-carbon double bond " The radical addition reaction product of, for example, the above-mentioned “compound having 3 to 10 mercapto groups in one molecule” and “acidic group, group having basic nitrogen atom, urea group, urethane group, coordination property” A group having an oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and at least one functional group selected from the group consisting of a hydroxyl group, and A method (thiol-ene reaction method) in which a compound having an elemental-carbon double bond is dissolved in an appropriate solvent and a radical generator is added thereto and added at about 50 ° C. to 100 ° C. is utilized. Obtained.

  Examples of suitable solvents used in the above method include “compounds having 3 to 10 mercapto groups in one molecule”, “acid groups, groups having basic nitrogen atoms, urea groups, urethane groups, A group having a coordinated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group and at least one functional group selected from the group consisting of a hydroxyl group, and a mercapto group; It can be arbitrarily selected depending on the solubility of the compound having a functional group capable of reacting (for example, a carbon-carbon double bond) and the resulting radical addition reaction product. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  As the radical generator, azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl peroxide And persulfates such as potassium persulfate and ammonium persulfate can be used.

In the present invention, the component (B) may be used alone or in combination of two or more.
The content of the component (B) in the ink composition of the present invention is preferably 1 to 100% by weight and more preferably 5 to 50% with respect to the amount of the component (A) (organic pigment) added.
When the amount of the component (B) is 1% by weight or more, good dispersibility is obtained, and a dispersion having a large particle size (aggregated) is not preferable. Moreover, it is preferable for it to be 100% by weight or less because an increase in viscosity due to the excess component (C) does not occur.
In the ink composition of the present invention, a known pigment dispersant can be used in combination with the component (B) as long as the effects of the present invention are not impaired. In this case, the content of the known pigment dispersant in the ink composition is preferably 50% by weight or less and more preferably 30% by weight or less with respect to the amount of the component (B) added. .

Examples of the known dispersants (pigment dispersants) include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meta ) Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanolamine, pigment derivative, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to its structure.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the surface of the pigment are preferable structures. On the other hand, the pigment derivative has an effect of promoting adsorption of the polymer dispersant by modifying the surface of the pigment.

  Specific examples of the known dispersant (pigment dispersant) include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group)”, 130, manufactured by BYK Chemie. (Polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, manufactured by EFKA Corporation ” 4010, 4165 (polyurethane-based), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (Phthalocyanine derivative), 6750 ( Zo pigment derivative) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fan Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ” “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725”, Kao, manufactured by Enomoto Kasei Co., Ltd. “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)”, “Aceta Min 86 (stearylamine acetate), Lubrizol "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end) , 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemical Co., Ltd., and the like.

<(C) Actinic radiation curable compound>
The ink composition of the present invention contains an actinic radiation curable compound (hereinafter also referred to as a polymerizable compound). The actinic radiation curable compound is not particularly limited as long as it is a compound that can be cured by causing a polymerization reaction or a crosslinking reaction upon irradiation with actinic radiation, and can be appropriately selected according to the purpose.
Although it can be used regardless of the type of monomer, oligomer, or polymer, it is known as a photocationically polymerizable monomer or photoradically polymerizable monomer that causes a polymerization reaction by a polymerization initiating species generated from a polymerization initiator described later. Various known polymerizable monomers are preferred.
The polymerizable compound that can be used in the present invention is preferably an addition polymerizable compound, and more preferably a radical polymerizable compound. In addition, as the polymerizable compound that can be used in the present invention, plural kinds of polymerizable compounds may be used, and it is also preferable to use a radical polymerizable compound and a cationic polymerizable compound in combination.

The said polymeric compound may be used individually by 1 type, and may use 2 or more types together in order to adjust reaction rate, ink physical property, cured film physical property, etc.
The polymerizable compound may be a monofunctional compound or a polyfunctional compound.

[Radically polymerizable compound]
As the polymerizable compound that can be used in the present invention, an addition polymerizable compound having at least one ethylenically unsaturated double bond can be preferably used.
The addition polymerizable compound having at least one ethylenically unsaturated double bond is preferably selected from compounds (monofunctional or polyfunctional compounds) having at least one terminal ethylenically unsaturated bond, more preferably two or more. Is.
Specifically, it can be appropriately selected from those widely known in the industrial field according to the present invention, for example, monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof, and Those having a chemical form such as a copolymer of
Specifically, the polymerizable compound preferably has a polymerizable group such as an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, or an internal double bond group (such as maleic acid) in the molecule. A compound having an acryloyl group or a methacryloyl group is preferable in that it can cause a curing reaction.

As the radical polymerizable compound, a polymerizable compound having a cyclic group is preferably used, and examples of the cyclic group include an aliphatic ring group, a heterocyclic group, and an aromatic ring group. The aliphatic cyclic group is more preferably a condensed polycyclic group in which two or more rings are condensed.
The radical polymerizable compound preferably has a polymerizable group selected from the group consisting of acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group and N-vinyl group as the polymerizable group.

-Radically polymerizable compound having a heterocyclic group-
Preferred examples of the compound having a heterocyclic group that can be suitably used in the present invention include N-vinyl lactams.
Preferable examples of N-vinyl lactams that can be used in the present invention include compounds represented by the following formula (A-1).

In formula (A-1), n represents an integer of 1 to 5, and n is 2 from the viewpoints of flexibility after the composition is cured, adhesion to a recording medium, and availability of raw materials. It is preferably an integer of 4 or less, more preferably n is 2 or 4, and particularly preferably n is 4, that is, N-vinylcaprolactam. N-vinylcaprolactam is preferable because it is excellent in safety, is generally available and can be obtained at a relatively low price, and provides particularly good curability and adhesion to a recording medium.
The N-vinyl lactams may have a substituent such as an alkyl group or an aryl group on the lactam ring, and may be linked with a saturated or unsaturated ring structure.

The ink composition of the present invention preferably contains 5% by weight or more of N-vinyl lactam, more preferably 5% by weight or more and 40% by weight or less, and more preferably 10% by weight or more and 40% by weight. % Or less is more preferable. It is preferable that the amount of N-vinyl lactam used be in the above range because it is excellent in curability, flexibility and adhesion to the recording medium.
N-vinyl lactams are compounds having a relatively high melting point. When the content of N-vinyl lactam is 40% by weight or less, good solubility is exhibited even at a low temperature of 0 ° C. or less, and the temperature range in which the ink composition can be handled is widened.
The N-vinyl lactams may be contained in the ink composition alone or in a plurality of kinds. In addition, when using 2 or more types of N-vinyl lactam as N-vinyl lactam, it is preferable that content of N-vinyl lactam exists in the said range as a total amount.

-Radical polymerizable compound having an aromatic ring group and radical polymerizable compound having an aliphatic ring group-
The radically polymerizable compound having an aromatic ring group and the radically polymerizable compound having an aliphatic ring group which are preferably used in the present invention will be described in detail.
In the present invention, examples of the compound having an aromatic ring group or an aliphatic ring group that can be suitably used include an ethylenically unsaturated compound represented by the following formula (5 ′).

In the above formula (5 ′), R ¹ represents a hydrogen atom or a methyl group.
n ¹ is an integer of 1 or more, preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.
X ¹ in the formula (5 ′) is (—C (O) O—) or (—C (O) bonded to the ethylenically unsaturated double bond represented by the formula (5 ′) at the carbon atom of the carbonyl group. NH-) represents a divalent linking group, and the divalent linking group further includes an ether bond (—O—), an ester bond (—C (O) O— or —OC (O) —), an amide A bond (—C (O) NH— or —NHC (O) —), a carbonyl bond (—C (O) —), an optionally substituted alkylene group having 20 or less carbon atoms, or a combination thereof Group may be bonded.
The divalent linking group is -C (O) O-, -C (O) NH-, or -C (O) O- or -C (O) NH- and an ether bond, an ester bond or a carbon number. It is more preferably a group in which 20 or less alkylene groups and a group in which two or more of these are combined are linked.
R ² in Formula (5 ′) is a group having at least one or more cyclic structures, an aromatic group containing a monocyclic aromatic group and / or a polycyclic aromatic group, a cycloalkane skeleton, an adamantane skeleton And an alicyclic hydrocarbon group having a norbornane skeleton. Further, the aromatic structure and the cyclic structure of the alicyclic hydrocarbon group may contain heteroatoms such as O, N, and S.

Preferred examples of the aromatic group represented by R ² in the formula (5 ′) include a polycyclic aromatic group having 2 to 4 rings in addition to a monocyclic aromatic phenyl group.
Specific examples of the polycyclic aromatic group include naphthyl group, anthryl group, 1H-indenyl group, 9H-fluorenyl group, 1H-phenenyl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, naphthacenyl group, tetraphenyl group, Preferred examples include biphenylenyl group, as-indacenyl group, s-indacenyl group, acenaphthylenyl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, chrysenyl group, and preadenyl group.

These aromatic groups may be aromatic heterocyclic groups containing heteroatoms such as O, N, and S. Specifically, furyl group, thienyl group, 1H-pyrrolyl group, 2H-pyrrolyl group, 1H-pyrazolyl group, 1H-imidazolyl group, isoxazolyl group, isothiazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazoyl group And monocyclic aromatic heterocyclic groups such as a tetrazoyl group.
In addition, thiantenyl group, benzofuranyl group, isobenzofuranyl group, chromenyl group, isochromenyl group, xanthenyl group, phenoxathiinyl group, indolizinyl group, isoindolyl group, indolyl group, indazolyl group, purinyl group, quinolidinyl group, isoquinolyl group, Quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, carbazolyl group, β-carboliyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, Examples thereof include polycyclic aromatic heterocyclic groups such as a phenothiazinyl group, a phenoxazinyl group, and a pyrrolidinyl group.
The aromatic group may have one or more substituents such as a halogen atom, a hydroxyl group, an amino group, a mercapto group, a siloxane group, and a hydrocarbon group having 30 or less carbon atoms. For example, you may form the cyclic structure containing hetero atoms, such as O, N, and S, by two or more substituents which an aromatic group has like phthalic anhydride and phthalimide anhydride.

R ² in formula (5 ′) may be an alicyclic hydrocarbon group. Moreover, the group which has an alicyclic hydrocarbon group containing hetero atoms, such as O, N, and S, may be sufficient.
The alicyclic hydrocarbon group may be a 3 to 12-membered cycloalkane or a group having a ring structure in which two or more of these cycloalkanes are condensed. Among these, cyclohexyl group, cyclopentyl group, cycloheptyl group, isobornyl group, norbornyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group, tricyclodecanyl group and the like can be preferably exemplified.
Specific examples of the alicyclic hydrocarbon group containing a heteroatom such as O, N, and S include a tetrahydrofuryl group, a pyrrolidinyl group, a pyrazolidinyl group, an imidazolidinyl group, an isoxazolidinyl group, and a pyranyl group. Thiopyranyl group, isothiazolidinyl group, piperidinyl group, piperazinyl group, morpholino group, thiomorpholino group and the like.
These alicyclic hydrocarbon groups and alicyclic hydrocarbon groups having a heteromonocycle have a halogen atom, a hydroxyl group, an amino group, a thiol group, a siloxane group, and a total carbon number that may further have a substituent. It is preferably a hydrocarbon group of 30 or less, a heterocyclic group containing a heteroatom such as O, N, or S, or an oxy group (═O) as a divalent substituent.

R ² in the formula (5 ′) may be a group having an adamantane skeleton represented by the following formula (I) or an alicyclic hydrocarbon group having a norbornane skeleton represented by (II).

R ³ and R ⁴ in formula (I) or formula (II) each independently represent a substituent, and can be bonded at any position on each alicyclic hydrocarbon structure. Further, q R ³ and r R ⁴ may be the same or different.
R ³ present in q and R ⁴ present in r may each independently be a monovalent or polyvalent substituent, and as a monovalent substituent, a hydrogen atom, a hydroxyl group, substituted or unsubstituted An amino group, a thiol group, a siloxane group, a hydrocarbon group or a heterocyclic group having a total carbon number of 30 or less which may have a substituent, or an oxy group (= O) as a divalent substituent. It is preferable.
The substitution number q of R ³ represents an integer of 0 to 5, and the substitution number r of R ⁴ represents an integer of 0 to 5.
Further, one carbon atom in the adamantane skeleton in the formula (I) may be substituted with a carbonyl bond (—C (O) —) and / or an ester bond (—C (O) O—). One carbon atom in the norbornane skeleton may be substituted with an ether bond (—O—) and / or an ester bond (—C (O) O—).

  The norbornane skeleton represented by the formula (II) may have a cyclic hydrocarbon structure as represented by (III). N in the formula (III) represents a cyclic hydrocarbon structure, and both ends thereof may be substituted at any position of the norbornane skeleton, and may be a monocyclic structure or a polycyclic structure. In addition to the hydrocarbon bond, the cyclic hydrocarbon structure may contain a carbonyl bond (—C (O) —) and / or an ester bond (—C (O) O—).

  The cyclic structure represented by the formula (III) is preferably a structure represented by the formula (IV), the formula (V) or the formula (VI).

In formula (IV), formula (V) and formula (VI), R ⁵ , R ⁶ and R ⁷ each independently represent a substituent, k represents an integer of 1 to 6, and s, t and u each represent R represents an integer of 0 to 5 independently, and s R ⁵ , t R ⁶ and u R ⁷ may be the same or different.
X ^{1 in} formula (5 ′) can be bonded at any position on each alicyclic hydrocarbon structure shown below in formula (IV), formula (V), or formula (VI).
R ⁵ , R ⁶ and R ⁷ in formula (IV), formula (V) or formula (VI) each independently represent a substituent, and each of the following fats in formula (IV), formula (V) or formula (VI) The bond can be made at any position on the cyclic hydrocarbon structure. The substituents in R ⁵ , R ⁶ and R ⁷ are synonymous with the substituents in R ³ and R ⁴ in formulas (I) to (III), and the preferred ranges are also the same.

  In the present invention, the radical polymerizable monomer includes phenyl group, naphthyl group, anthracenyl group, pyridinyl group, tetrahydrofurfuryl group, piperidinyl group, cyclohexyl group, cyclopentyl group, cycloheptyl group, isobornyl group, tricyclodecanyl group, etc. Those having a group having the following cyclic structure are preferred.

  The radical polymerizable monomer that can be used in the present invention is preferably norbornyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl ( (Meth) acrylate, cyclodecyl (meth) acrylate, dicyclodecyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-benzyl (meth) acrylate, phenoxyethyl (meth) ) Acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, ethylene oxide (EO) modified cresol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene glycol (meta ) Acrylate, N-phthalimidoethyl (meth) acrylate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, N-cyclohexylacrylamide, N- (1,1-dimethyl-2-phenyl) ethylacrylamide, N -Diphenylmethylacrylamide, N-phthalimidomethylacrylamide, N- (1,1'-dimethyl-3- (1,2,4-to Azole-1-yl)) propyl acrylamide, can be exemplified 5- (meth) acryloyloxy-methyl-5-ethyl-1,3-oxa-cyclohexane.

Furthermore, the preferable specific example of the radically polymerizable monomer which can be used for this invention is shown to the following M-1 to M-56.
In some of the following exemplary compounds, the hydrocarbon chain is described by a simplified structural formula in which the symbols of carbon (C) and hydrogen (H) are omitted.

  The radically polymerizable compound having a cyclic group can be used alone or in combination of two or more. Among these, it is preferable to use a radically polymerizable compound having at least a heterocyclic group, and it is preferable to use N-vinyl lactams as the radically polymerizable compound having a heterocyclic group. Further, it is preferable to further use a radical polymerizable compound having an aromatic ring group or a radical polymerizable compound having an aliphatic ring group, a radical polymerizable compound having a heterocyclic group, a radical polymerizable compound having an aromatic ring group, and It is preferable to use a radically polymerizable compound having an aliphatic ring group in combination.

In the present invention, the radical polymerizable compound having a cyclic group is preferably contained in an amount of 10% by weight or more, more preferably 10% by weight to 90% by weight, and still more preferably 30% by weight. It is -90 weight%, Most preferably, it is 50 weight%-85 weight%.
The radically polymerizable compound having a heterocyclic group is preferably contained in the ink composition in an amount of 5% by weight to 40% by weight, and more preferably 10 to 40% by weight. Further, the radical polymerizable compound having an aliphatic ring group and the radical polymerizable compound having an aromatic ring group are preferably contained in an amount of from 5 to 90% by weight in the ink composition, and from 20 to 85% by weight. It is more preferable that it is contained in an amount of 40 to 80% by weight.

Moreover, the following radically polymerizable compounds can also be used.
For example, a photocurable material using a photopolymerizable composition described in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, etc. It has been known.

  Examples of the polymerizable compound having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, esters thereof and salts thereof , Anhydrides having ethylenically unsaturated groups, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated urethane (meth) acrylic monomers or prepolymers, epoxy monomers or prepolymers (Meth) acrylic acid esters such as urethane monomers or prepolymers are preferably used.

  Specifically, (poly) ethylene glycol mono (meth) acrylate, (poly) ethylene glycol (meth) acrylate methyl ester, (poly) ethylene glycol (meth) acrylate ethyl ester, (poly) ethylene glycol (meth) acrylate phenyl Ester, (poly) propylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate phenyl ester, (poly) propylene glycol (meth) acrylate methyl ester, (poly) propylene glycol (meth) acrylate ethyl ester, (Poly) propylene glycol diglycidyl ether acrylic acid adduct, neopentyl glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, Poly) tetramethylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, PO (propylene oxide) adduct di (meth) acrylate of bisphenol A, ethoxylated neopentyl glycol diacrylate, propoxylated neo Pentyl glycol diacrylate, EO (ethylene oxide) adduct di (meth) acrylate of bisphenol A, EO modified pentaerythritol triacrylate, PO modified pentaerythritol triacrylate, EO modified pentaerythritol tetraacrylate, PO modified pentaerythritol tetraacrylate, EO modified Dipentaerythritol tetraacrylate, PO-modified dipentaerythritol tetraacrylate, EO-modified trimethylol Lopan triacrylate, PO-modified trimethylolpropane triacrylate, EO-modified tetramethylolmethane tetraacrylate, PO-modified tetramethylolmethane tetraacrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, isooctyl Acrylate, n-lauryl acrylate, n-tridecyl acrylate, n-cetyl acrylate, n-stearyl acrylate, isomyristyl acrylate, isostearyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, penta Erythritol triacrylate, pentaerythritol tetraacrylate, di Acrylic acid derivatives such as pentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, isoamyl acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2 -Ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, isooctyl methacrylate, n-lauryl methacrylate, n-tridecyl methacrylate, n-cetyl methacrylate, n-stearyl methacrylate, allyl methacrylate, glycidyl methacrylate, Benzyl methacrylate, dimethylaminomethyl Methacrylate derivatives such as methacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Derivatives of allyl compounds, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 2-ethylhexyl-diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxypivalic acid neopentyl glycol diacrylate, 2-acryloyloxyethylphthalic acid, nonylphenol EO adduct acrylate Methoxy-polyethylene glycol acrylate, tetramethylol methane triacrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, dimethylol tricyclodecane diacrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinic acid, Modified glycerin triacrylate, bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, phenoxy-polyethylene glycol acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, dipentaerythritol hexaacrylate, pentaerythritol triacrylate tolylene Isocyanate urethane prepolymer, lactone-modified flexible acrylate, butoxyethyl acrylate, pen Taerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, and more specifically, Yamashita Tsubame three edition "Cross-linking agent handbook" (1981, Taiseisha); Kato Kiyomi edition "UV / EB curing handbook (raw material edition)" (1985, Polymer publication society); Radtech study group edition "UV / EB curing technology" Application and Market "page 79 (1989, CMC); Eiichiro Takiyama's" Polyester resin handbook "(1988, Nikkan Kogyo Shimbun) etc. Gender or crosslinkable monomers may be used oligomers and polymers.

  These acrylate compounds can lower the viscosity relatively than the polymerizable compounds conventionally used in UV curable inks, provide stable ink ejection properties, and good polymerization sensitivity and adhesion to the recording medium. Therefore, it is preferable.

Furthermore, it is also preferable to use a vinyl ether compound as the radical polymerizable compound. Suitable vinyl ether compounds include, for example, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol. Di- or trivinyl ether compounds such as divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octade Monovinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-O-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, etc. Examples include vinyl ether compounds.
Of these vinyl ether compounds, divinyl ether compounds and trivinyl ether compounds are preferable from the viewpoints of curability, adhesion, and surface hardness, and divinyl ether compounds are particularly preferable. A vinyl ether compound may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.

Among these, (meth) acrylates and (meth) acrylamides are preferable from the viewpoint of curing speed, tetrafunctional or higher (meth) acrylates are more preferable, and polyfunctional (in terms of viscosity of the ink composition). It is preferable to use a combination of (meth) acrylate with monofunctional or bifunctional (meth) acrylate and (meth) acrylamide.
The content of the polymerizable compound in the ink composition is preferably 50 to 95% by weight, more preferably 60 to 92% by weight, particularly 70 to 90% by weight, based on the total solid content of the ink composition. preferable.

[Cationically polymerizable monomer]
Examples of the cationic polymerizable monomer that can be used as the polymerizable compound include, for example, JP-A Nos. 6-9714, 2001-31892, 2001-40068, 2001-55507, 2001-310938, and 2001-310937. An epoxy compound, a vinyl ether compound, an oxetane compound and the like described in each publication such as JP-A No. 2001-220526 are preferable.

The epoxy compound may be a monofunctional epoxy compound or a polyfunctional epoxy compound.
Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, and 1,3-butadiene mono. Oxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. Can be mentioned.

Examples of the polyfunctional epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl. Ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2 -(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) Methyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 '-Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) , Epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Serine triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-di Examples include epoxy octane, 1,2,5,6-diepoxycyclooctane, and the like.
Among these epoxy compounds, an aromatic epoxy compound and an alicyclic epoxy compound are preferable, and an alicyclic epoxy compound is particularly preferable in terms of excellent curing speed.

The vinyl ether compound may be a monofunctional vinyl ether compound or a polyfunctional vinyl ether compound.
Examples of the monofunctional vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4 -Methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl Ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloro Examples thereof include ethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxy polyethylene glycol vinyl ether, and the like.

Examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F alkylene oxide. Divinyl ethers such as divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide addition And polyfunctional vinyl ethers such as pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.
Among these vinyl ether compounds, di- or trivinyl ether compounds are preferable, and divinyl ether compounds are particularly preferable in terms of curability, adhesion to a recording medium, surface hardness of the formed image, and the like.

The oxetane compound means a compound having an oxetane ring, and preferred examples thereof include known oxetane compounds described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217.
In the present invention, the oxetane compound is preferably a compound having 1 to 4 oxetane rings in its structure. When such a compound is used, it becomes easy to maintain the viscosity of the ink composition in a good handling property range, and it is possible to obtain high adhesion of the cured ink to a recording medium. Is advantageous.

The oxetane compound may be a monofunctional oxetane compound or a polyfunctional oxetane compound.
Examples of the monofunctional oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro -[1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanyl) Methoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) Ether, 2-ethylhexyl (3-ethyl-3-oxe) Nylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, Dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxy Ethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, and the like.

  Examples of the polyfunctional oxetane compound include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)). Bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1 , 3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3 Ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3 -Ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl- 3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3- Til-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentane Kis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A Bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3 -Ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, and the like.

In addition to these, as the oxetane compound, compounds described in detail in paragraphs [0021] to [0084] of JP-A-2003-341217 can also be suitably used in the present invention.
Among the oxetane compounds described above, in the present invention, a compound having 1 to 2 oxetane rings is preferable from the viewpoint of viscosity and adhesiveness of the ink composition.

  When a cationically polymerizable compound is used in the ink composition of the present invention, the above-mentioned cationically polymerizable compound may be used alone or in combination of two or more. From the standpoint of effectively suppressing the shrinkage, it is preferable to use at least one oxetane compound in combination with at least one compound selected from an epoxy compound and a vinyl ether compound.

<Other ingredients>
The ink composition of the present invention may contain other components appropriately selected according to the purpose, in addition to the C component, the polymerizable compound and the pigment.
Examples of the other components include polymerization initiators, sensitizing dyes, co-sensitizers, resins, surfactants, ultraviolet absorbers, antioxidants, anti-fading agents, ejection stabilizers, adhesion improvers, and leveling. Examples thereof include additives and matting agents. These may be used individually by 1 type and may use 2 or more types together.

(Polymerization initiator)
In the present invention, when the ink is cured using photoactive rays such as ultraviolet rays, a polymerization initiator is contained. As a polymerization initiator that can be used in the present invention, a known polymerization initiator can be used, and a radical polymerization initiator is preferably used. The polymerization initiator that can be used in the present invention may be used alone or in combination of two or more. Moreover, you may use together a radical polymerization initiator and a cationic polymerization initiator.
The polymerization initiator that can be used in the ink composition of the present invention is a compound that absorbs external energy and generates a polymerization initiating species. External energy used for initiating polymerization is roughly divided into heat and actinic radiation, and a thermal polymerization initiator and a photopolymerization initiator are used, respectively. Examples of the active radiation include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays.

-Radical polymerization initiator-
Examples of radical polymerization initiators that can be used in the present invention include (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, (d) organic peroxides, (e) thios. Compound, (f) hexaarylbiimidazole compound, (g) ketoxime ester compound, (h) borate compound, (i) azinium compound, (j) metallocene compound, (k) active ester compound, (l) carbon halogen bond And (m) an alkylamine compound. These radical polymerization initiators may use the above compounds (a) to (m) alone or in combination. The radical polymerization initiator in the present invention is preferably used alone or in combination of two or more.

  Preferable examples of (a) aromatic ketones, (b) acylphosphine compounds, and (e) thio compounds are “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY”, J. P. FOUASSIER, J. F. RABEK (1993), pp. 191 Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in 77-117. More preferable examples include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, α-substituted benzoin compounds described in JP-B-47-22326, Benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, JP-B-60-26403, JP-A Benzoin ethers described in JP-A-62-81345, JP-B-1-34242, US Pat. No. 4,318,791, α-aminobenzophenones described in European Patent 0284561A1, JP-A-2-21152 P-Di (dimethylaminobenzoyl) benze Thio-substituted aromatic ketones described in JP-A-61-194062, acylphosphine sulfides described in JP-B-2-9597, acylphosphines described in JP-B-2-9596, and JP-B-63-61950 Thioxanthones, and coumarins described in JP-B-59-42864.

  (C) As aromatic onium salt compounds, elements of Groups 15, 16 and 17 of the periodic table, specifically N, P, As, Sb, Bi, O, S, Se, Te, or I fragrances Group onium salts are included. For example, iodonium salts described in European Patent No. 104143, US Pat. No. 4,837,124, Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-96514, European Patent Nos. 370693, 233567, and 297443 are disclosed. The diazonium salts described in the specifications of U.S. Pat. Nos. 2,974,279, 279210, and 422570, U.S. Pat. Nos. 3,902,144, 4,933,377, 4,760013, 4,734,444, and 2,833,827. Benzenediazonium which may have a substituent), diazonium salt resins (formaldehyde resin of diazodiphenylamine, etc.), N-alkoxypyridinium salts, etc. (for example, US Pat. No. 4,743,528, JP-A-63) -138345, JP-A-63 No. 142345, JP-A-63-142346, and JP-B-46-42363, specifically 1-methoxy-4-phenylpyridinium tetrafluoroborate, etc. The compounds described in JP-A 52-147277, 52-14278, and 52-14279 are preferably used. Generates radicals and acids as active species.

  (D) The organic peroxide includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include 3,3 ′, 4,4′-tetra- ( t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-hexylperoxycarbonyl) ) Benzophenone, 3,3 ′, 4,4′-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (cumylperoxycarbonyl) benzophenone, 3,3 ′, Perester ester compounds such as 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone and di-t-butyldiperoxyisophthalate Thing is preferable.

  (F) Examples of hexaarylbiimidazole compounds include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2 , 2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5 ' Tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 Examples include ', 5,5'-tetraphenylbiimidazole.

  (G) Examples of the ketoxime ester compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxyiminopentane-3. -One, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminotan-2-one, 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.

  (H) Examples of the borate compound include compounds described in US Pat. Nos. 3,567,453, 4,343,891, European Patents 109,772, and 109,773. Can be mentioned.

  (I) Examples of azinium salt compounds include JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143537, and JP-B-46-42363. The compound group which has NO bond of each gazette description can be mentioned.

  (J) Examples of metallocene compounds include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, and JP-A-2-4705. And the iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopenta And dienyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium.

  (K) Examples of the active ester compound include the specifications of European Patent Nos. 0290750, 046083, 156153, 271851, and 0388343, U.S. Pat. Nos. 3,901,710, and 4,181,531. Nitrobenzol ester compounds described in JP-A-60-198538 and JP-A-53-133022, European Patents 0199672, 84515, 199672, 0441115, and 0101122. No. 4,618,564, U.S. Pat. No. 4,371,605, and U.S. Pat. No. 4,431,774, and JP-A 64-18143, JP-A-2-245756, and JP-A-4-365048. Iminosulfonate compound, Japanese Examined Patent Publication No. 62-6223, Japanese Examined Publication No. 63 No. 14340, and compounds, and the like described in the JP-A No. 59-174831.

  (L) Preferable examples of the compound having a carbon halogen bond include, for example, compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, Examples thereof include compounds described in Japanese Utility Model Publication No. 53-133428, compounds described in German Patent No. 3337024, and the like.

  Further, compounds described in J. Org. Chem., 29, 1527 (1964) by FC Schaefer et al., Compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, and the like can be mentioned. it can. A compound as described in German Patent No. 2641100, a compound as described in German Patent No. 3333450, a compound group as described in German Patent No. 3021590, or a compound group as described in German Patent No. 3021599, etc. Can be mentioned.

-Cationic polymerization initiator-
In the ink composition of the present invention, when a cationic polymerizable compound is used in combination, a cationic polymerization initiator is preferably used in combination.

First, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ salt of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, phosphonium, etc. be able to. Secondly, sulfonated products that generate sulfonic acid can be mentioned. Thirdly, a halide that generates hydrogen halide can also be used. Fourthly, an iron allene complex can be mentioned.

In the ink composition of the present invention, the total amount of the polymerization initiator used is preferably 0.01 to 35% by weight, more preferably 0.8%, based on the total amount of the polymerizable compound containing N-vinyl lactams. It is 5 to 20% by weight, more preferably 1.0 to 15% by weight. The ink composition can be cured at 0.01% by weight or more, and a cured film having a uniform degree of curing can be obtained at 35% by weight or less, which is preferable.
Moreover, when using the sensitizing dye mentioned later for the ink composition of this invention, the total usage-amount of a polymerization initiator is the weight ratio of a polymerization initiator: sensitizing dye with respect to a sensitizing dye, Preferably it is 200: It is 1-1: 200, More preferably, it is the range of 50: 1 to 1:50, More preferably, it is the range of 20: 1 to 1: 5.

[Sensitizing dye]
In particular, when used for ink jet recording, a sensitizing dye may be added to the ink composition of the present invention in order to absorb specific actinic radiation and promote decomposition of the polymerization initiator. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with the polymerization initiator, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the polymerization initiator undergoes a chemical change and decomposes to generate radicals, acids or bases.
Examples of preferred sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
Polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), squalium (for example, squalium) ), Coumarins (eg 7-diethylamino-4-methylcoumarin).

  More preferable examples of the sensitizing dye include compounds represented by the following formulas (IX) to (XIII).

In the formula (IX), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² forms a basic nucleus of the dye together with the adjacent A ¹ and the adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus of the dye. Good. W represents an oxygen atom or a sulfur atom.

In formula (X), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in Formula (IX).

In the formula (XI), A ₂ represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye together with adjacent A ₂ and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a monovalent non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In formula (XII), A ³ and A ⁴ each independently represent —S—, —NR ⁶² — or —NR ⁶³ —, and R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted or represents an unsubstituted aryl group, L to ^5, L ⁶ are each independently, together with the adjacent a ^3, a ⁴ and adjacent carbon atoms represents a nonmetallic atom group necessary for forming a basic nucleus of a dye, R ⁶⁰ , R ⁶¹ each independently represents a hydrogen atom or a monovalent non-metallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring.

In the formula (XIII), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or ═NR ⁶⁷ . R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ each represent an aliphatic or aromatic ring. Can be combined to form.

Preferable specific examples of the compounds represented by formulas (IX) to (XIII) include (E-1) to (E-20) shown below.
In some of the following exemplary compounds, the hydrocarbon chain is described by a simplified structural formula in which the symbols of carbon (C) and hydrogen (H) are omitted.

  The content of the sensitizing dye in the ink composition of the present invention is appropriately selected depending on the purpose of use, but generally it is preferably 0.05 to 4% by weight based on the weight of the whole ink composition. .

[Co-sensitizer]
The ink composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye to actinic radiation or suppressing polymerization inhibition of the polymerizable compound by oxygen.
Examples of such a co-sensitizer include amines such as MR Sander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Examined Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102. No. 52-134692, No. 59-138205, No. 60-84305, No. 62-18537, No. 64-33104, No. 64-33104, Research Disclosure No. . Examples include compounds described in No. 33825, and specific examples include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Donors, sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250387 (diethyl phosphite, etc.), Si-H described in JP-A-8-54735 , Ge—H compounds and the like.
The content of the co-sensitizer in the ink composition of the present invention is appropriately selected depending on the purpose of use, but is generally 0.05 to 4% by weight with respect to the weight of the entire ink composition. preferable.

[Surfactant]
A surfactant is preferably added to the ink composition of the present invention in order to provide stable ejection properties for a long time.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. An organic fluoro compound may be used instead of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826.
The content of the surfactant in the ink composition of the present invention is appropriately selected depending on the purpose of use, but in general, it is preferably 0.0001 to 1% by weight with respect to the total weight of the ink composition. .

[Ultraviolet absorber]
In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance of the obtained image and preventing discoloration.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194843, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492 and 56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in US Pat. No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, and so-called fluorescent brighteners.
The addition amount is appropriately selected according to the purpose, but generally it is preferably 0.5 to 15% by weight in terms of solid content.

〔Antioxidant〕
An antioxidant can be added to improve the stability of the ink composition. Examples of the antioxidant include European published patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443. JP, 54-85535, 62-262417, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples thereof include those described in Kaihei 3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by weight in terms of solid content.

[Anti-fading agent]
In the ink composition of the present invention, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of the metal complex anti-fading agent include nickel complexes and zinc complexes. No. 17643, Nos. VII to I, J. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of representative compounds described in JP-A-62-215272, pages 127 to 137 can be used. .
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by weight in terms of solid content.

[Conductive salts]
Conductive salts such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate, and dimethylamine hydrochloride can be added to the ink composition of the present invention for the purpose of controlling ejection properties.

〔solvent〕
In order to improve the adhesion to the recording medium, it is also effective to add a very small amount of an organic solvent to the ink composition of the present invention.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether Examples include ether solvents.
In this case, it is effective to add the solvent within the range that does not cause the problem of solvent resistance and VOC. % Range.

[Polymer compound]
Various polymer compounds can be added to the ink composition of the present invention in order to adjust film physical properties. High molecular compounds include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, vinyl resins, acrylic resins. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination. Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, as a copolymer composition of the polymer compound, a copolymer containing “carboxyl group-containing monomer”, “alkyl methacrylate ester” or “alkyl acrylate ester” as a structural unit is also preferably used.

In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, polymerization to inhibit the adhesion to recording media such as polyolefin and PET, and the like, The tackifier which does not do can be contained.
As the tackifier, specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, 5-6p (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms). An ester with an alcohol having, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid with an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifier resin having a polymerizable unsaturated bond.

<Ink physical properties>
In the present invention, the viscosity at 25 ° C. of the ink composition is preferably 50 mPa or less, and more preferably 40 mPa · s or less, in consideration of dischargeability. Preferably, it is 3 mPa · sec to 50 mPa · sec, more preferably 5 mPa · s to 40 mPa · s, and still more preferably 7 mPa · s to 30 mPa · s. Moreover, it is preferable that the viscosity in discharge temperature (for example, 25-80 degreeC, Preferably 25-50 degreeC) is 3-15 mPa * s, More preferably, it is 3-13 mPa * s. It is preferable that the composition ratio of the ink composition of the present invention is appropriately adjusted so that the viscosity is in the above range. By setting the viscosity at room temperature high, even when a porous recording medium is used, ink penetration into the recording medium can be avoided, and uncured monomers and odors can be reduced. Furthermore, it is preferable that ink bleeding at the time of ink droplet landing can be suppressed, and as a result, the image quality is improved.
The viscosity can be measured using, for example, a conical plate type rotational viscometer (E type viscometer).

The surface tension of the ink composition of the present invention at 25 ° C. is preferably 20 to 35 mN / m. More preferably, it is 23-33 mN / m. When recording on various recording media such as polyolefin, PET, coated paper, and non-coated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and the wettability is preferably 35 mN / m or less.
The surface tension can be measured using, for example, a Wilhelmy method surface tension meter or a Du Nouy surface tension meter.

<Manufacturing>
There is no restriction | limiting in particular as a manufacturing method of the ink composition of this invention, According to the objective, it can select suitably, For example, it can manufacture by mixing each above-mentioned component. In addition, the said mixing can be performed according to a well-known method using a well-known mixer etc.

<Use>
The ink composition of the present invention can be suitably used as an ink for various image recordings, and can be particularly suitably used as an ink composition for inkjet recording. In this case, the ink composition is printed on a recording medium by an ink jet printer, and then the printed ink composition (recorded image) is irradiated with the actinic radiation to be cured and image recording is performed. .
The image recorded matter (printed matter) obtained using the ink composition of the present invention is excellent in the strength of the image portion because the image portion is cured by irradiation with the active radiation such as ultraviolet rays. Therefore, in addition to image recording (image formation), it can be suitably used for various applications such as formation of an ink receiving layer (image portion) of a lithographic printing plate.

(Inkjet recording method and inkjet recording apparatus)
The ink composition of the present invention is used for inkjet recording.
In the inkjet recording method of the present invention, the ink composition of the present invention is ejected onto a recording medium (support, recording material, etc.) for inkjet recording, and actinic radiation is applied to the ink composition ejected onto the recording medium. It is a method of forming an image by irradiating and curing the ink.

More specifically, the inkjet recording method of the present invention comprises (a ¹ ) a step of ejecting the ink composition of the present invention onto a recording medium, and (b ¹ ) actinic radiation on the ejected ink composition. And a step of curing the ink composition.
By including the steps (a ¹ ) and (b ¹ ), the ink jet recording method of the present invention forms an image with the ink composition cured on the recording medium.

In the step (a ¹ ) in the ink jet recording method of the present invention, an ink jet recording apparatus described in detail below can be used.

<Inkjet recording apparatus>
There is no restriction | limiting in particular as an inkjet recording device used for the inkjet recording method of this invention, The well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and can be used. That is, any known inkjet recording apparatus including a commercially available product can eject ink onto a recording medium in the step (a ¹ ) of the inkjet recording method of the present invention.
Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including an ink supply system, a temperature sensor, and an actinic radiation source.
The ink supply system includes, for example, an original tank containing the ink composition of the present invention, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The piezo-type inkjet head has a multi-size dot of 1 to 100 pl, preferably 8 to 30 pl, for example, 320 × 320 to 4000 × 4000 dpi, preferably 400 × 400 to 1600 × 1600 dpi, and more preferably 720 × 720 dpi. It can drive so that it can discharge with the resolution of. In the present invention, dpi represents the number of dots per 2.54 cm.

  As described above, since it is desirable that the radiation-curable ink, like the ink composition of the present invention, has a constant temperature for the ink to be ejected, heat insulation and heating are performed from the ink supply tank to the inkjet head portion. It can be carried out. The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors at each piping site and perform heating control according to the ink flow rate and the environmental temperature. The temperature sensor can be provided near the ink supply tank and the nozzle of the inkjet head. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of thermal energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

Using the ink jet recording apparatus, the ink composition of the present invention is ejected by heating the ink composition to preferably 25 to 80 ° C., and preferably 25 to 50 ° C., so that the viscosity of the ink composition is 3 It is preferable to carry out after lowering to ˜15 mPa · s, preferably 3 to 13 mPa · s. In particular, it is preferable to use an ink composition having an ink viscosity at 25 ° C. of 50 mPa · s or less as the ink composition of the present invention, since it can be discharged satisfactorily. By using this method, high ejection stability can be realized.
A radiation curable ink composition such as the ink composition of the present invention generally has a higher viscosity than a water-based ink usually used in ink jet recording inks, and therefore has a large viscosity fluctuation due to temperature fluctuations during ejection. The ink viscosity fluctuation has a great influence on the change of the droplet size and the change of the droplet discharge speed, and causes the image quality deterioration. Therefore, it is necessary to keep the temperature of the ink at the time of ejection as constant as possible. Therefore, in the present invention, it is appropriate that the control range of the ink temperature is ± 5 ° C. of the set temperature, preferably ± 2 ° C. of the set temperature, more preferably ± 1 ° C. of the set temperature.

Next, the step (b ¹ ) of curing the ink composition by irradiating the discharged ink composition with actinic radiation will be described.
The ink composition ejected on the recording medium is cured by irradiation with actinic radiation. This is because the polymerization initiator contained in the ink composition of the present invention is decomposed by irradiation with actinic radiation to generate radicals, acids, bases, and other starting species, and the function of the starting species is polymerization of a radical polymerizable compound. This is because the reaction occurs and is accelerated. At this time, if a sensitizing dye is present together with the polymerization initiator in the ink composition, the sensitizing dye in the system absorbs actinic radiation to be in an excited state, and promotes decomposition of the polymerization initiator by contacting with the polymerization initiator. And a more sensitive curing reaction can be achieved.

  Here, α rays, γ rays, electron beams, X rays, ultraviolet rays, visible light, infrared rays, or the like can be used as the active radiation used. Although the peak wavelength of actinic radiation is based also on the absorption characteristic of a sensitizing dye, it is preferable that it is 200-600 nm, for example, it is more preferable that it is 300-450 nm, and it is further more preferable that it is 350-420 nm.

In addition, the polymerization initiation system of the ink composition of the present invention has sufficient sensitivity even with a low output actinic radiation. Accordingly, it is appropriate that the exposure surface illuminance is 10 to 4,000 mW / cm ² , preferably 20 to 2,500 mW / cm ² .

Mercury lamps and gas / solid lasers are mainly used as actinic radiation sources, and mercury lamps and metal halide lamps are widely known as light sources used for curing UV photocurable ink jet recording inks. Yes. However, from the viewpoint of environmental protection, mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, LED (UV-LED) and LD (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are expected as light sources for photo-curable ink jets.
Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit actinic radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic radiation source particularly preferred in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength at 350 to 420 nm.
Incidentally, it is preferable that maximum illumination intensity of the LED on a recording medium is 10 to 2,000 mW / cm ^2, more preferably 20 to 1,000 mW / cm ^2, particularly preferably 50 to 800 mW / cm ² .

The ink composition of the present invention is suitably irradiated with such actinic radiation for, for example, 0.01 to 120 seconds, preferably 0.1 to 90 seconds.
Actinic radiation irradiation conditions and a basic irradiation method are disclosed in JP-A-60-132767. Specifically, the light source is provided on both sides of the head unit including the ink ejection device, and the head unit and the light source are scanned by a so-called shuttle method. Irradiation with actinic radiation takes a certain time (for example, 0.01 to 0.5 seconds, preferably 0.01 to 0.3 seconds, more preferably 0.01 to 0.15 seconds) after ink landing. Will be done. In this way, by controlling the time from ink landing to irradiation to an extremely short time, it is possible to prevent the ink that has landed on the recording medium from spreading before curing. Further, since the ink can be exposed to the porous recording medium before the ink penetrates to a deep part where the light source does not reach, the residual unreacted monomer can be suppressed, and as a result, the odor can be reduced. Therefore, it is preferable.
Further, the curing may be completed by another light source that is not driven. WO99 / 54415 pamphlet discloses a method using an optical fiber and a method of applying a collimated light source to a mirror surface provided on the side surface of the head unit and irradiating the recording unit with UV light as an irradiation method. The curing method can also be applied to the ink jet recording method of the present invention.

By adopting the ink jet recording method as described above, the dot diameter of the landed ink can be kept constant even on various recording media having different surface wettability, and the image quality is improved. In addition, in order to obtain a color image, it is preferable to superimpose in order from the color with the lowest brightness. By superimposing the inks in the order of low lightness, the irradiation line can easily reach the lower ink, and good curing sensitivity, reduction of residual monomers, reduction of odor, and improvement of adhesion can be expected. In addition, irradiation can be performed by discharging all colors and collectively exposing, but exposure for each color is preferable from the viewpoint of promoting curing.
In this manner, the ink composition of the present invention can form an image on the surface of a recording medium by being cured with high sensitivity by irradiation with actinic radiation.

<Recording medium>
The recording medium on which the ink composition of the present invention is ejected to record an image is not particularly limited and can be appropriately selected according to the purpose. Papers such as ordinary uncoated paper and coated paper Examples thereof include various non-absorbable resin materials used for so-called soft packaging, or resin films obtained by molding the non-absorbent resin materials. Examples of the resin film include PET film, OPS film, OPP film, ONy film, PVC film, PE film, TAC film, polycarbonate film, acrylic film, ABS film, polyacetal film, PVA film, rubber film, Etc. Further, metals, glasses and the like can be used as the recording medium.

(Printed matter)
What was obtained by curing the ink composition of the present invention is the printed material of the present invention. The printed material is a material obtained by ejecting and curing the ink composition of the present invention on the recording medium. Is preferred. At this time, the ejection is performed by ink jet recording using an ink jet printer.
In the printed matter of the present invention, the ink composition used for image recording is the ink composition of the present invention, and contains fine pigment particles uniformly and stably dispersed. It is a high image, has excellent weather resistance, and can be suitably used in a wide range of fields.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples.
In the following description, “parts” means “parts by weight” unless otherwise specified.

The materials used in the present invention are as shown below.
・ HEUCO GREEN 600703K (CI Pigment Green 7); manufactured by Heubach ・ Monastral GREEN GN-C (CI Pigment Green 7); manufactured by Heubach ・ Monastral GREEN GNX-C (C.I. Pigment Green 7) ); Made by Heubach, Monastral GREEN GBX-C (CI Pigment Green 7); made by Heubach, made by HOSTAPERM GREEN GG01 (C.I. Pigment Green 7), made by Clariant, Inc. CI Pigment Green 7); made by Clariant, HOSTAPERM GREEN GNX-TS (CI Pigment Green 7); made by Clariant, PV Fast GREEN GNX (CI Pigment Green 7); Clariant, Novotex GREEN GNX (CI Pigment Green 7); Clariant, Fastogen GREEN S (CI Pigment Green 7); DIC, Fastogen GREEN SF (C.I. Pigment Green 7); DIC Corporation, Phthalocyanine GREEN B308 (C.I. Pigment Green 7); Sanyo Pigment Corporation, Phthacyanine GREEN SAX (C.I. Pigment Green 7);・ Cyanine GREEN 2G-550-D (CI Pigment Green 7); Dainichi Seika Co., Ltd. ・ Cyanine GREEN 2GO (CI Pigment Green 7); Dainichi Seika Co., Ltd. ・ Cyanine GREEN PBN-1 (C.I. Pigment Green 7); Toyo Ink Corporation, HELIOGEN BLUE L8605 (C.I. Pigment Green 7); BASF Corporation, HELIOGEN BLUE K8730 (C.I. Pigment Green 7); BASF • HELIOGEN BLUE D8725 (CI Pigment Green 7); BASF • HELIOGEN BLUE L9361 (CI Pigment Green 36); BASF • Irgalite GREEN 6G (C.I. Pigment Green 36); HOSTAPER GREEN 8G (C.I. Pigment Green 36) manufactured by CSC; Fastogen GREEN 2KY (C.I. manufactured by Clariant) I. Pigment Green 36); DIC Corporation, Lionol GREEN 2YS (CI Pigment Green 36); Toyo Ink Corporation, Lionol GREEN 6YK (CI Pigment Green 36); Toyo Ink Co., Ltd.

HOSTAPERM VIOLET RL-NF (CI Pigment Violet 23); Clariant Corporation HOSTAPERM VIOLET RL02 (CI Pigment Violet 23); Clariant Corporation HOSTAPERM VIOLET BL (CI Pigment Violet 23); Clariant's HOSTAPERM VIOLET P-RL (CI Pigment Violet 23); Clariant's HOSTAPERM VIOLET RLspec (CI Pigment Violet 23); Clariant's HOSTAPERM VIOLET RLspec-TS (CI Pigment Violet 23); made by Clariant, PV Fast Violet RL (CI Pigment Violet 23); Clarian • PV Fast Violet BLP (CI Pigment Violet 23); Clariant, Novotex Violet BL-PC VP 2429 (CI Pigment Violet 23); Clariant, Novotex Violet BL VP 2435 (C.I. CI Pigment Violet 23); Clariant, Fastogen Super Violet RN (C. I. Pigment Violet 23); DIC, Fastogen Super Violet RNS (C. I. Pigment Violet 23); RN-SU-02 (C.I. Pigment Violet 23); DIC Corporation, Fastogen Super Violet RVS (C.I. Pigment Violet 23); DIC Corporation, Fastogen Super Violet RXE (CI Pigment Violet 23); DIC Corporation, Fastogen Super Violet RXS (CI Pigment Violet 23); DIC Corporation, Lionogen Violet R6100 CI Pigment Violet 23); Toyo Ink Co., Ltd./Lionogen Violet R6200 (CI Pigment Violet 23); Toyo Ink Co., Ltd./Oriental Fast Violet BL (CI Pigment Violet 23); Paliogen Violet L 5890 (CI Pigment Violet 23); manufactured by BASF, Chromophthal Violet GT (C.I. I. Pigment Violet 23); CSC, Chromophthal Violet B (CI Pigment Violet 37); CSC

・ Novoperm Orange HL (C.I. Pigment Orange 36); Clariant ・ Novoperm Orange HL70 (C.I. Pigment Orange 36); Clariant ・ Novoperm Orange HL70-NF (C.I. Pigment Orange 36); Clariant's Novo Orange Orange HL70-TS (CI Pigment Orange 36); Clariant's Novo Orange Orange HL 71 (CI Pigment Orange 36); Clariant's Symuler Fast Orange 4183H (C.I. Pigment Orange 36) Orange 36); manufactured by DIC, Chromofine Orange 3700L (CI Pigment Orange 36); manufactured by Dainichi Seika Co., Ltd., Lionog n Orange R-F (CI Pigment Orange 36); Novoperm Red HFG (C.I. Pigment Orange 38) manufactured by Toyo Ink Co .; Hostarm Orange HGL (C.I. Pigment Orange 60) manufactured by Clariant Made by company

・ DisperBYK-168 (dispersant, manufactured by BYK Chemie)
・ Solsperse 32000 (dispersant, manufactured by Noveon)
・ Fancrill 512A (equivalent to Exemplified Compound M- 10 , manufactured by Hitachi Chemical Co., Ltd.)
・ N-vinylcaprolactam (manufactured by Aldrich)
Actilane 421 (propoxylated neopentyl glycol diacrylate, A
cros)
・ NK ester AMP-10G (phenoxyethyl acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
-Firstcure ST-1 (polymerization inhibitor, manufactured by Chem First)
・ Lucirin TPO (photoinitiator, manufactured by BASF)
・ Benzophenone (Photoinitiator, Wako Pure Chemical Industries, Ltd.)
・ Irgacure 184 (photoinitiator, manufactured by CSC)
・ BYK 307 (surfactant, manufactured by BYK Chemie)
-Firstcure ITX (sensitizer, manufactured by Chem First)

(Synthesis of polymer compound represented by formula (1))
<Synthesis of mercaptan compound having a functional group A ^1>
As shown below, chain transfer agents B-1 and B-2 (mercaptan compounds represented by the above-described formula (3)) were synthesized.

[Synthesis Example B-1]
Dipentaerythritol tetrakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.] 7.83 parts, and the following compound having a functional group A ¹ and having a carbon-carbon double bond (A-1) 6.51 parts was dissolved in 33.45 parts of 1-methoxy-2-propanol and heated to 70 ° C. under a nitrogen stream. To this, 0.06 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Furthermore, 0.06 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 30% solution of a mercaptan compound (chain transfer agent B-1) shown below was obtained.

[Synthesis Example B-2]
In Synthesis Example B-1, 6.51 parts of compound (A-1) having functional group A ¹ and having a carbon-carbon double bond, 33.45 parts of 1-methoxy-2-propanol Except that the compound (A-2) having a functional group A ¹ and a carbon-carbon double bond was changed to 5.80 parts and 31.81 parts of 1-methoxy-2-propanol. In the same manner as in Example 1, a 30% solution of a mercaptan compound (chain transfer agent B-2) shown below was obtained.

<Synthesis of polymer compounds>
Subsequently, the polymer compound of the present invention described above was synthesized as shown below.
[Synthesis Example C-1]
A mixed solution of 19.11 parts of a 30% solution of chain transfer agent B-1 described in Synthesis Example B-1 and 20 parts of methyl methacrylate was heated to 80 ° C. under a nitrogen stream. To this, 0.013 part of 2,2′-azobis (isobutyronitrile) [AIBN, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Furthermore, 0.013 part of AIBN was added and reacted at 80 ° C. for 3 hours under a nitrogen stream. Then, it cooled to room temperature and diluted with acetone. After reprecipitation using a large amount of methanol, vacuum drying was performed to obtain 13 parts of a polymer compound (C-1: polystyrene equivalent weight average molecular weight 12,000) shown below.

[Synthesis Example C-2]
In Synthesis Example C-1, Synthesis Example C-1 except that 19.11 parts of a 30% solution of chain transfer agent B-1 were changed to 9.56 parts and 0.013 parts of AIBN were changed to 0.007 parts. In the same manner as above, 14 parts of a polymer compound (C-2: polystyrene-equivalent weight average molecular weight 20,000) shown below was obtained.

[Synthesis Example C-3]
In Synthesis Example C-1, except that 20 parts of methyl methacrylate were changed to 19.5 parts of butyl methacrylate and 8.5 parts of 2-hydroxyethyl methacrylate, the same as in Synthesis Example C-1. Then, 13 parts of a solid compound (C-3: polystyrene-equivalent weight average molecular weight 13,000) shown below was obtained.

[Synthesis Example C-4]
The same as in Synthesis Example C-1, except that 19.11 parts of chain transfer agent B-1 were changed to 18.18 parts of chain transfer agent B-2 in Synthesis Example C-1. 11 parts by weight of a solid of a polymer compound (C-4: polystyrene equivalent weight average molecular weight 13,000) was obtained.

[Synthesis Example C-5]
In Synthesis Example C-1, 19.11 parts of chain transfer agent B-1 was changed to 18.1 parts by weight of chain transfer agent B-2, and 20 parts of methyl methacrylate was changed to 19.5 parts of n-butyl methacrylate. The polymer compound shown below (C-5: weight average molecular weight of 16,000 in terms of polystyrene) was the same as in Synthesis Example C-1, except that the amount was changed to 8.5 parts of 2-hydroxyethyl methacrylate. 11 parts by weight of a solid was obtained.

(Preparation of mill base A1)
HEUCO GREEN 600703K 300 parts by weight Actilane 421 (acrylate monomer manufactured by Akcros) 500 parts by weight Polymer compound (C-1) 200 parts by weight The above components were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of mill bases A2 to A30)
Mill bases A2 to A30 were prepared in the same manner as the mill base A1, except that the pigments and polymer compounds were changed to the pigments and polymer compounds shown in Table 1 below.

(Preparation of mill base B1)
HOSTAPERM VIOLET RL-NF 300 parts by weight Actilane 421 (Akcros acrylate monomer) 500 parts by weight
Polymer Compound (C-1) 200 parts by weight The above components were mixed with stirring to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of mill bases B2 to B27)
Mill bases B2 to B27 were prepared in the same manner as the mill base B1 except that the pigments and the polymer compounds were changed to the pigments and polymer compounds shown in Table 2 below.

(Preparation of mill base C1)
Symuler Fast Orange 4183H 300 parts by weight Actilane 421 (Acrys acrylate monomer) 500 parts by weight
Polymer Compound (C-1) 200 parts by weight The above components were mixed with stirring to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of mill bases C2 to C19)
Millbases C2 to C19 were prepared in the same manner as the millbase C1, except that the pigments and polymer compounds were changed to the pigments and polymer compounds shown in Table 3 below.

[Example 1-1]
The following components were stirred with a high-speed water-cooled stirrer to obtain an inkjet ink. The viscosity was 17 mPa · s.
(Ink composition)
・ Milbase A1 6.0 parts ・ Fancrill 512A 35.4 parts ・ N-vinylcaprolactam 25.0 parts ・ NK ester AMP-10G 20.0 parts ・ First cure ST-1 0.05 part ・ Lucirin TPO (BASF Corporation) 8.5 parts · Benzophenone (photoinitiator) 3.0 parts · Irgacure 184 (CSC photoinitiator) 2.0 parts · BYK 307 (BYK Chemie surfactant) 0.05 Parts ・ Dimethylaminoethyl acrylate 0.1 parts

(Evaluation of ink)
Ink jet recording was performed using the obtained ink composition.
The curability, storage stability, ejection properties (continuous ejection reliability and nozzle clogging recovery), flexibility and substrate adhesion were evaluated. The evaluation results are shown in Table 1.

<Storage stability>
The ink compositions of Examples and Comparative Examples were held at 60 ° C. for 4 weeks.
The evaluation criteria are shown below.
4: Less than 5% increase in viscosity, no change in pigment particle size 3: Less than 5-10% increase in viscosity, no change in pigment particle size 2: Over 10% to less than 30% increase in viscosity, with pigment particle size 1: 30% increase in viscosity Above, pigment particle size available

<Inkjet image recording method>
Using an ink before aging and each ink composition after aging, recording on a recording medium was performed using an inkjet recording experimental apparatus having a piezo-type inkjet nozzle. The ink supply system was composed of an original tank, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The ink supply tank was insulated and heated from the inkjet head portion. Temperature sensors were provided near the ink supply tank and the nozzle of the ink jet head, respectively, and temperature control was performed so that the nozzle portion was always 45 ° C. ± 2 ° C. The piezo-type inkjet head was driven so that 8 to 30 pl multi-size dots could be ejected at a resolution of 720 × 720 dpi. After landing, UV light was condensed to an exposure surface illuminance of 1,630 mW / cm ² , and the exposure system, main scanning speed, and ejection frequency were adjusted so that irradiation started 0.1 seconds after ink landed on the recording medium. . Further, the integrated light amount irradiated to the image was set to 4,500 mJ / cm ² . A HAN250NL high-cure mercury lamp (manufactured by GS Yuasa Corporation) was used as the ultraviolet lamp. In the present invention, dpi represents the number of dots per 2.54 cm. As a recording medium, an ester film E5000 (film thickness 125 μm, manufactured by Toyobo Co., Ltd.) was used.

<Method of measuring curing sensitivity (curability)>
In accordance with the ink jet recording method, a solid image having an average film thickness of 12 μm is drawn, the degree of stickiness of the image is evaluated by palpation on the image surface after ultraviolet irradiation, and the change before and after aging is evaluated according to the following criteria: did.
3 ・ ・ ・ No change before and after aging.
2 ... There is some fluctuation before and after aging, and there is some stickiness after aging.
1... Fluctuates greatly before and after the passage of time, and after the passage of time, the uncured ink is not hardened to transfer to the hand

<Flexibility evaluation method: Bending test>
In this example, a bending test was performed as a method for evaluating the flexibility of the cured film before and after storage.
According to the inkjet ink jet image recording method, an ester film E5000 (film thickness 125 μm, manufactured by Toyobo Co., Ltd.) was used as a recording medium, and three solid images having an average film thickness of 12 μm, 24 μm, and 36 μm were drawn. In the bending test, the recording material on which the image was formed was bent once at 25 ° C. and evaluated by the presence or absence of cracks in the image area. In general, when the average film thickness is increased, distortion applied to the image portion when the image portion is bent increases, and cracks are likely to occur. That is, by testing whether the image portion is cracked with a thicker film thickness, a measure of flexibility can be obtained.
The evaluation criteria are as follows.
4: Cracks do not occur in samples having an average film thickness of 12 μm, 24 μm, and 36 μm.
3: Cracks do not occur in samples having an average film thickness of 12 μm and 24 μm.
2: Cracks do not occur in the sample having an average film thickness of 12 μm, but cracks occur in the bent portion of the image portion in the sample having an average film thickness of 24 μm.
1: In all samples having an average film thickness of 12 μm, 24 μm, and 36 μm, a crack occurs in the bent portion of the image portion.

<Base material adhesion evaluation method: cross hatch test (EN ISO 2409)>
Using PET (ester film E5000, film thickness 125 μm, manufactured by Toyobo Co., Ltd.) as a recording medium, a solid image having an average film thickness of 12 μm was drawn on each substrate in accordance with the inkjet ink jet image recording method. Thereafter, a cross-hatch test (EN ISO 2409) was performed on each printed matter.

<Viscosity measurement method>
In this example, the viscosity was measured using a B-type viscometer: Brookfield LVDV-I (manufactured by Brookfield) at 25 ° C. and a rotor rotation speed of 20 rpm.

<Dischargeability>
The following two types (A, B) were evaluated using the above-described ink jet drawing apparatus.
[Evaluation A (Continuous discharge reliability)]
Before the ink jet apparatus was operated, the liquid circulation with the liquid of the present invention was repeated for 15 minutes to remove the ink remaining in the ink contact portion in the apparatus. Thereafter, continuous use for 8 hours was carried out, and the number of nozzles causing drawing defects (non-ejection, twisting, etc.) was counted.
4 ... No ejection failure 3 ... Ejection failure 3 nozzles or less 2 ... Ejection failure 3 nozzles or more and less than -10 nozzles 1 ... Ejection failure 10 nozzles or more All of these were counted per head.

[Evaluation B (Reset nozzle clogging)]
In evaluation A, liquid circulation and discharge with the liquid of the present invention was repeatedly performed for 15 minutes on a head having 10 or more defective discharges, ink was supplied again, drawing was performed, and the number of non-discharge nozzles was confirmed.
4 ... No ejection failure 3 ... Ejection failure 3 nozzles or less 2 ... Ejection failure 3 nozzles or more and less than -10 nozzles 1 ... Ejection failure 10 nozzles or more All of these were counted per head.

[Examples 1-2 to 1-28 and Comparative Examples 1-1 and 1-2]
An inkjet ink was obtained in the same manner as in Example 1-1, except that the mill base A1 was changed to the mill base shown in Table 4. The viscosity was 17-22 mPa · s.
Further, ink jet recording was performed in the same manner as in Example 1-1, and evaluation was performed in the same manner. The results are shown in Table 4.

[Example 2-1]
An ink jet ink was obtained in the same manner as in Example 1-1 except that the mill base A1 was changed to the mill base B1. The viscosity was 18 mPa · S.
Further, ink jet recording was performed in the same manner as in Example 1-1, and evaluation was performed. The results are shown in Table 5.

[Examples 2-2 to 2-25, Comparative Examples 2-1 and 2-2]
An inkjet ink was obtained in the same manner as in Example 2-1, except that the mill base B1 was changed to the mill base shown in Table 5. The viscosity was 17-22 mPa · s.

[Example 3-1]
An ink jet ink was obtained in the same manner as in Example 1-1 except that the mill base A1 was changed to the mill base C1. The viscosity was 19 mPa · S.
Further, ink jet recording was performed in the same manner as in Example 1-1, and evaluation was performed. The results are shown in Table 6.

[Examples 3-2 to 3-17, Comparative examples 3-1 and 3-2]
An inkjet ink was obtained in the same manner as in Example 3-1, except that the mill base C1 was changed to the mill base shown in Table 6. The viscosity was 17-22 mPa · s.

Example 4
The color reproducibility of the printed image was evaluated using the process ink and the ink compositions obtained in Example 1-1, Example 2-1, and Example 3-1.
FIG. 1 shows the maximum range of color reproduction (a ^* , b ^* ) measured in Example 4.
As process inks, cyan (EI made by Celicol), magenta (EI made by Celicol), yellow (EI made by Celicol), and black (EI made by Celicol) were used. The solid line in FIG. 1 is process color print image data. All 950 color patches are allocated evenly using synthetic ink (processed by Oji Tac Co., Ltd.) on the synthetic paper (made by Oji Tac Co., Ltd.). It is data. This indicates the maximum range of process ink color reproduction (a ^* , b ^* ). The dotted line indicates the maximum range of hues (a ^* , b ^* ) of the pantone color sample book.
In FIG. 1, the results of measuring the hues of the printed images obtained using the green, violet, and orange ink compositions prepared in Examples 1-1, 2-1, and 3-1 are indicated by ◇. The print image data are all primary colors, and are eight-level shade patch data.
Here, hue (a ^* , b ^* ) and lightness (L) were measured by SPM100-II manufactured by Gretag.
As a result, it has become clear that reproducibility can be obtained even in hues that have been difficult to reproduce with conventional process inks.

FIG. 1 shows the maximum range of color reproduction (a ^* , b ^* ) measured in Example 4.

Claims (13)

At least one organic pigment exhibiting an orange, violet, or green color,
A polymer compound represented by the following formula (1), and
Contains an actinic radiation curable compound ,
An inkjet ink composition comprising a compound represented by the following formula (A-1) as the actinic radiation curable compound .

[Wherein, R ¹ represents an (m + n) -valent organic linking group, and R ² represents a single bond or a divalent organic linking group. A ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and It represents a monovalent organic group having a group selected from the group consisting of a hydroxyl group, and n A ^{1 s} may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton. ]

[Wherein n represents an integer of 1 or more and 5 or less. ] The inkjet ink composition according to claim 1, wherein the polymer compound is represented by the following formula (2).

[Wherein R ³ represents an (m + n) -valent organic linking group, and R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. A ² is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and It represents a monovalent organic group having a group selected from the group consisting of a hydroxyl group, and n A ^{2 s} may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ² represents a polymer skeleton. ] The inkjet ink composition according to claim 1 or 2, wherein the organic pigment is at least one selected from the group shown below.
C. I. Pigment orange 36, 38, 43, 71,
C. I. Pigment violet 23, 32, 37, 39, and C.I. I. Pigment Green 7, 36, 37 The inkjet ink composition according to any one of claims 1 to 3, wherein the organic pigment is at least one selected from the group shown below.
C. I. Pigment orange 36,
C. I. Pigment violet 23, 37 and C.I. I. Pigment Green 7 The ink composition for inkjet according to any one of claims 1 to 4, wherein the organic pigment is a dioxane type compound represented by the formula (A).

In formula (A), R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or a monovalent group.   The dioxazine type compound is C.I. I. Pigment violet 23 or C.I. I. The inkjet ink composition according to claim 5, which is CI Pigment Violet 37.   The inkjet ink composition according to any one of claims 1 to 6, wherein the compound represented by the formula (A-1) is N-vinylcaprolactam.   The inkjet ink composition according to any one of claims 1 to 7, further comprising an ethylenically unsaturated compound represented by the following formula (5 ').

(Wherein R ¹ Represents a hydrogen atom or a methyl group, n ¹ Is an integer greater than or equal to 1 and X ¹ Is a divalent group containing (—C (O) O—) or (—C (O) NH—) bonded to the carbon atom of the carbonyl group to the ethylenically unsaturated double bond represented by the formula (5 ′). Represents a linking group, R ² Is a group represented by the following formula (IV) or a group represented by the formula (V). )

(In the formulas (IV) and (V), R ^Five And R ⁶ Each independently represents a substituent, s and t each independently represent an integer of 0 to 5, and s Rs exist. ^Five And t R ⁶ May be the same or different. )   Furthermore, the ink composition for inkjets as described in any one of Claims 1-8 containing the ethylenically unsaturated compound represented by the following formula | equation (5 '').

(Wherein R ^{1 '} Represents a hydrogen atom or a methyl group, n ^{1 '} Is an integer greater than or equal to 1 and X ^{1 '} Is a divalent compound containing (—C (O) O—) or (—C (O) NH—) bonded to the carbon atom of the carbonyl group to the ethylenically unsaturated double bond represented by the formula (5 ″). Represents a linking group of R ^{2 '} Is an aromatic group. )   An ink set comprising cyan, magenta, yellow and black inks as the ink composition for inkjet according to any one of claims 1 to 9 and process ink. (A ¹⁾ onto a recording medium, a step of discharging the inkjet ink composition according to any one of Claims 1-9 and,
(B ¹⁾ discharged with actinic radiation by irradiating the ink composition for inkjet, the ink jet recording method characterized by comprising the steps of curing the ink composition. The actinic radiation is an ultraviolet ray irradiated by a light emitting diode that generates an ultraviolet ray having an emission peak wavelength in the range of 350 to 420 nm and a maximum illuminance on the recording medium surface of 10 to 2,000 mW / cm ^2. The inkjet recording method according to claim 11 . Printed matter recorded by the inkjet recording method according to claim 11 or 12 .

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