CN101519555A - Inkjet ink composition, and inkjet recording method and printed material employing same - Google Patents

Abstract

An inkjet ink composition is provided that includes at least one type of organic pigment exhibiting an orange, violet, or green color, at least one type selected from the group consisting of polymer compounds derived from a monomer represented by specific Formulae and a polymer represented by a specific Formula, and an actinic radiation-curable compound.

Description

Ink composition for ink jet and ink jet recording method and the print of using said composition

Technical field

The present invention relates to be suitable as ink composition for ink jet, ink jet recording method that ink-vapor recording uses and the print that obtains by above-mentioned ink jet recording method.At length say, relate to by shining active radioactive rays high sensitivity ground and solidify, even be suitable for ink composite, ink jet recording method that ink-vapor recording uses and the print of using it what ink solidification after fixing thing also had a sufficient flexibility.

Background technology

As the image recording process that on printing mediums such as paper, forms image according to viewdata signal, known electronic photographic means, subliming type and fusion thermal transfer mode, ink-jetting style etc.Wherein, above-mentioned ink-jetting style can be implemented with cheap device, and, because only directly form image thinking spray oil extraction China ink in the necessary image portion on printing medium, so can effectively use printing ink, running cost is low, noise is few in addition, is good as the image recording mode.Utilize above-mentioned ink-jetting style, not only also can print on the common paper but also on non-absorptive printing mediums such as plastic tab, metal sheet.

As one of above-mentioned ink-jetting style, there is application to come the recording mode of solidified ink-vapor recording by shining active radioactive rays with the solidified nature ink composite.Utilize this method, can be after printing the direct irradiation radioactive rays, droplet of ink is solidified, and then forms distinct image.

In above-mentioned solidified nature ink composite, in order to have formed the high precise image of excellent color reproducing performance, demanding pigment-dispersing and ageing stability.Usually, for the high tinting strength of color harmony of giving the ink composite distinctness, need the pigment miniaturization, particularly with regard to the ink composite that ink-vapor recording is used, because spray row's droplet of ink brings bigger influence for the sharpness of image, so need to use the spray discharge opeing amount of dripping also less and than the also trickle particle of thickness of the ink solidification film that forms by this ink composite.

Therefore, the pigment that general requirement has sufficient flowability and a miniaturization stably disperses and the excellent more ink composite of ageing stability of colo(u)rant dispersion, in the past, has proposed various suggestions for the dispersion agent that is used to obtain stable dispersible pigment dispersion.

For example, in order to improve the affinity with pigment, proposed the ink composite (TOHKEMY 2003-119414 communique, TOHKEMY 2004-18656) of pigment derivative as dispersion agent; For specific pigments such as phthalocyanine, quinacridones, use to have the ink composite (TOHKEMY 2003-321628 communique) of the polymkeric substance of basic group as dispersion agent; Contain poly-(ethyleneimine)-gather the specific monomer of dispersion agent such as (12-oxystearic acid) graftomer and this dispersion agent of dissolving and with an organic solvent ink composite (TOHKEMY 2004-131589 communique) not.

In addition, also require to realize desired color reproduction zone, disclose a kind of radiation-curing type jetted ink (Japanese Unexamined Patent Application Publication 2003-531223 communique) that has used characteristic printing ink such as pigment orange and Pigment green for this reason.

Summary of the invention

The purpose of this invention is to provide can be by ink composite that is suitable for the ink-vapor recording purposes that shines active radiation-curing and high-quality ink jet recording method and the print of using said composition, the dispersiveness of the micropigment of described ink composite and excellent in stability thereof, the color reproduction excellence can form the high quality images with the high tinting strength of distinct color harmony.

In order to solve above-mentioned problem, people of the present invention have carried out repeatedly attentively research, found that pigment-dispersing excellence when using specific polymkeric substance as pigment dispersing agent, even and prolonged preservation, through also suppressing the ink composite that dispersion stabilization descends effectively after the temperature variation repeatedly.

Above-mentioned problem of the present invention is by following＜1 〉,＜14 and＜16 described in means solve.Also put down in writing preferred embodiment simultaneously＜2～＜13 and＜15.

＜1〉a kind of ink composition for ink jet is characterized in that, contains: present at least a of orange, purple or green pigment dyestuff; Be selected from least a in the polymkeric substance of the monomeric macromolecular compound that comes from following formula (1-1) expression, the monomeric macromolecular compound that comes from following formula (2-1) expression and following formula (3-1) expression; And active radiation-curable compound,

In the above-mentioned formula (1-1), R ¹The alkyl of expression hydrogen atom, replacement and unsubstituted alkyl any, R ²The expression alkylidene group, W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-and phenylene is any, X represents-CO-,-NHCO-,-OC (=O)-,-CH (OH) CH ₂-and-SO ₂-any, R ³, R ⁴Expression monovalence substituting group, R ³And R ⁴Can interconnection formation ring texture, m, n are respectively 0 or 1 independently,

In the above-mentioned formula (2-1), R ¹Expression hydrogen atom, the alkyl of replacement and any, the R of unsubstituted alkyl ²The expression alkylidene group, W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-and phenylene is any, X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OC (=O) NH-,-CO-,-SO ₂-,-CH (OH) CH ₂NH-,-CH (OH) CH ₂S-,-SO ₂NH-and-NHCO-any, Y represents-NR ⁵-,-O-and-S-any, R ⁵Represent any of hydrogen atom, alkyl and aryl, R ³, R ⁴Expression monovalence substituting group, R ³And R ⁴Can interconnection formation ring texture, m, n are respectively 0 or 1 independently.

In the above-mentioned formula (3-1), R ¹Organic linking group of expression (m+n) valency, R ²Expression singly-bound or the organic linking group of divalent, A ¹Expression contains by being selected from the 1 valency organic group that organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, carbonatoms are at least a pigment adsorption structure that constitutes in alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl more than 4, n A ¹, R ²Can distinguish identical or differently independently, m represents 1～8, and n represents 2～9, and m+n is 3～10, P ¹The expression polymer backbone, m P ¹Can be identical or different.

＜2〉above-mentioned＜1〉described in ink composition for ink jet, the monomer of wherein above-mentioned formula (1-1) expression is the monomer of following formula (1-2) expression,

In the above-mentioned formula (1-2), R ³, R ⁴Expression monovalence substituting group, R ³And R ⁴Can interconnection formation ring texture.

＜3〉above-mentioned＜1〉described in ink composition for ink jet, the monomer of wherein above-mentioned formula (2-1) expression is the monomer of following formula (2-2) expression,

In the above-mentioned formula (2-2), R ¹The alkyl of expression hydrogen atom, replacement and unsubstituted alkyl any, Y, Z be expression-NR independently respectively ⁵-,-O-and-S-any, R ⁵Represent any of hydrogen atom, alkyl and aryl, R ³, R ⁴Expression monovalence substituting group, R ³And R ⁴Can interconnection formation ring texture.

＜4〉above-mentioned＜1〉described in ink composition for ink jet, the monomer of wherein above-mentioned formula (2-1) expression is the monomer of following formula (2-3) expression,

In the above-mentioned formula (2-3), R ¹The alkyl of expression hydrogen atom, replacement and unsubstituted alkyl any, Y represents-NR ⁵-,-O-and-S-any, R ⁵Represent any of hydrogen atom, alkyl and aryl, R ³, R ⁴Expression monovalence substituting group, R ³And R ⁴Can interconnection formation ring texture.

＜5〉above-mentioned＜1〉described in ink composition for ink jet, wherein for above-mentioned polymkeric substance, in the above-mentioned formula (3-1), A ¹Expression contains that to be selected from organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups and carbonatoms be 1 at least a valency organic group in the alkyl more than 4.

＜6〉above-mentioned＜1〉described in ink composition for ink jet, wherein for above-mentioned polymkeric substance, in the above-mentioned formula (3-1), P ¹The polymer backbone of expression is to come to be selected from least a in polymer of vinyl monomer or multipolymer, ester based polymer, ether based polymer, carbamate based polymer, acid amides based polymer, epoxy based polymer, siloxane-based polymers and their modifier or the multipolymer.

＜7〉above-mentioned＜1〉described in ink composition for ink jet, the polymkeric substance of its Chinese style (3-1) expression is the polymkeric substance of following formula (3-2) expression,

In the above-mentioned formula (3-2), R ³Organic linking group of expression (m+n) valency, R ⁴, R ⁵Represent the organic linking group of singly-bound or divalent independently of one another, A ²Expression contains by being selected from the 1 valency organic group that organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, carbonatoms are at least a pigment adsorption structure that constitutes in alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl more than 4, n A ², R ⁴Can distinguish identical or differently independently, m represents 1～8, and n represents 2～9, and m+n is 3～10, P ²The expression polymer backbone, m P ², R ⁵Can distinguish identical or different independently.

＜8〉above-mentioned＜7〉described in ink composition for ink jet, wherein for above-mentioned polymkeric substance, in the above-mentioned formula (3-2), A ²Be to contain that to be selected from organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups and carbonatoms be 1 at least a valency organic group in the alkyl more than 4.

＜9〉above-mentioned＜7〉described in ink composition for ink jet, wherein for above-mentioned polymkeric substance, in the above-mentioned formula (3-2), P ²The polymer backbone of expression is to come to be selected from least a in polymer of vinyl monomer or multipolymer, ester based polymer, ether based polymer, carbamate based polymer, acid amides based polymer, epoxy based polymer, siloxane-based polymers and their modifier or the multipolymer.

＜10〉above-mentioned＜1〉described in ink composition for ink jet, wherein above-mentioned pigment dyestuff is to be selected from least a in the group shown below:

C.I. pigment orange 36,38,43,71;

C.I. pigment Violet 23,32,37,39; And

C.I. pigment Green 7,36,37.

＜11〉above-mentioned＜1〉described in ink composition for ink jet, wherein above-mentioned pigment dyestuff is to be selected from least a in the group shown below:

C.I. pigment orange 36;

C.I. pigment Violet 23,37; And

C.I. pigment Green 7.

＜12〉above-mentioned＜1〉described in ink composition for ink jet, wherein above-mentioned pigment dyestuff is following formula (A) expression De dioxazine type compound,

In the above-mentioned formula (A), R ¹～R ¹⁰Represent hydrogen atom, halogen atom (fluorine atom, chlorine atom, bromine atoms, iodine atom) or 1 valency group respectively independently.

＜13〉above-mentioned＜12〉described in ink composition for ink jet, wherein above-mentioned dioxazine type compound is C.I. pigment Violet 23 or C.I. pigment violet 37.

＜14〉a kind of ink jet recording method is characterized in that, comprises following operation: (a ¹) above-mentioned＜1 of spray row on printing medium described in the operation of ink composition for ink jet; And (b ¹) shine active radioactive rays to spray row's ink composition for ink jet, make this ink composite solidified operation.

＜15〉above-mentioned＜14〉described in ink jet recording method, wherein above-mentioned active radioactive rays are to be the scope of 350～420nm and to produce the highest illumination on the printing medium surface be 10～2000mW/cm by the glow peak wavelength ²The ultraviolet ray of ultraviolet photodiode irradiation.

＜16〉a kind of print, it is by above-mentioned＜14〉described ink jet recording method carries out record.

According to the present invention, can provide and to come solidified to be suitable for the ink composite of ink-vapor recording purposes and high-quality ink jet recording method and the print of using said composition by shining active radioactive rays, the dispersiveness of the micropigment of described ink composition and excellent in stability thereof, the color reproduction excellence can form the high quality images with the high tinting strength of distinct color harmony.

Description of drawings

Fig. 1 is the color reproduction (a that measures among the embodiment 1-4 ^*, b ^*) maximum region.

Fig. 2 is the color reproduction (a that measures among the embodiment 2-4 ^*, b ^*) maximum region.

Fig. 3 is the color reproduction (a that measures among the embodiment 3-4 ^*, b ^*) maximum region.

Embodiment

Ink composition for ink jet of the present invention (among the present invention, is also referred to as " ink composite " or " printing ink " to " ink composition for ink jet ".) be characterised in that, contain: (A) present at least a of orange, purple or green pigment dyestuff; (B) come from the monomeric macromolecular compound (being also referred to as " polymkeric substance of formula (1-1) ") that above-mentioned formula (1-1) is represented; And (C) active radiation-curable compound.In addition, can also contain other composition selected of coming as required to suit.Above-mentioned ink composite can solidify when the active radioactive rays of irradiation (among the present invention, being also referred to as active energy ray).

As above-mentioned active radioactive rays (active energy ray), so long as by its irradiation can give can make in the above-mentioned ink composite produce the energy that curing reaction causes kind active radioactive rays just, be not particularly limited, can suit to select according to purpose, can list for example alpha-ray, gamma-rays, X ray, ultraviolet ray, visible light, electron beam etc.Among the present invention, consider preferred ultraviolet ray and electron beam in the above-mentioned active radioactive rays, preferred especially ultraviolet ray from easy the to be acquired viewpoint of solidifying sensitivity and device.

(ink composition for ink jet)

Below, ink composition for ink jet of the present invention is described.

＜(A) present orange, purple or green pigment dyestuff 〉

Ink composite of the present invention contains and presents at least a of orange, purple or green pigment dyestuff (the following pigment dyestuff that also abbreviates as).In addition, ink composite of the present invention is preferably and contains any one the ink composite that presents in orange, purple or the green pigment dyestuff.Here, the ink composite of the present invention that contains orange pigment dyestuff is also referred to as the orange ink composition, the ink composite of the present invention of the pigment dyestuff that contains purple is also referred to as the purple ink composition, the ink composite of the present invention that contains green pigment dyestuff is also referred to as the green ink composition.

In addition, for example when containing the pigment dyestuff of purple, the pigment dyestuff of purple can be used alone, and also can more than two kinds and use.Can also in ink composite, also use the tinting material (preferred pigment dyestuff) that presents other color as required.

Ink composition for ink jet of the present invention is preferably used as the printing ink group of being made up of multiple ink composition for ink jet, at this moment, be the printing ink group that comprises at least a ink composite that is selected from orange ink composition, purple ink composition and green ink composition.Be more preferably the printing ink group that comprises orange ink composition, purple ink composition and green ink composition.

In addition, also preferred and the versicolor ink composite that presents cyan, magenta, yellow and black and so on and with and form the printing ink group, preferred as required and with the ink composite that presents white.

The pigment dyestuff that ink composite of the present invention contained is the pigment dyestuff that presents at least a color in purple, orange, the green at least.

Describedly here present orange pigment dyestuff and be defined as, be coated with its dispersion liquid and the tone (a of the film that obtains ^*, b ^*) be " b ^*＜2a ^*+ 20 and b ^*A ^*-20 (a ^*0, b ^*0) " scope in pigment dyestuff.Equally, the described pigment dyestuff that presents purple is defined as, and is coated with its dispersion liquid and the tone (a of the film that obtains ^*, b ^*) be " b ^*〉-2a ^*-20 and b ^*＜0.5a ^*+ 10 (a ^*0, b ^*＜0) pigment dyestuff in the scope " describedly presents green pigment dyestuff and is defined as, and is coated with its dispersion liquid and the tone (a of the film that obtains ^*, b ^*) be " b ^*＜-a ^*+ 20 and b ^*〉-0.25a ^*(a ^*＜0) pigment dyestuff in the scope ".In addition, tone (a ^*, b ^*) measurement can use Gretag corporate system SPM100-II.

The pigment concentration of the pigment dyestuff dispersion liquid that here uses in order to estimate tone is preferably 1～30wt%.The particle diameter of the pigment dyestuff in the dispersion liquid (volume average particle size) is not particularly limited, but considers from the viewpoint of the influence that suppresses scattering of light, is preferably below the 1 μ m, more preferably below the 500nm, more preferably below the 200nm.Need only painted fewly as dispersion medium, perhaps do not have just paintedly, be not particularly limited preferably water, general solvent, commercially available monomer etc.The operation of making dispersion liquid is not particularly limited, and can use technique known.Because fairly simple, so can preferably use Ball milling, the dispersion of pearl mill or ultrasonic dispersing etc.Also preferred in dispersion liquid, suit to use commercially available tensio-active agent or pigment dispersing agent.

As the base material of coating dispersion liquid, be preferably the base material of white.So long as the base material of white is just, be not particularly limited, for example, can preferably use for example commercially available white coated paper, white synthetic paper etc.Means as the coating dispersion liquid are not particularly limited, and for example, excellent Tu Fa etc. are simple, can preferably use.

Consider from the viewpoint that obtains broad color reproduction,, more preferably be coated with its dispersion liquid and the tone (a of the film that obtains as presenting orange pigment dyestuff ^*, b ^*) be " b ^*＜2a ^*And b ^*A ^*(a ^*0, b ^*0) " scope in pigment dyestuff.Equally, consider,, more preferably be coated with its dispersion liquid and the tone (a of the film that obtains as the pigment dyestuff that presents purple from the viewpoint that obtains broad color reproduction ^*, b ^*) be " b ^*〉-2a ^*And b ^*＜0.5a ^*(a ^*0, b ^*＜0) pigment dyestuff in the scope ".As presenting green pigment dyestuff, more preferably be coated with its dispersion liquid and the tone (a of the film that obtains ^*, b ^*) be " b ^*＜-a ^*(a ^*0, b ^*＜0) pigment dyestuff in the scope ".

Present the pigment dyestuff of any color in purple, orange, the green so long as satisfy above-mentioned tone just, be not particularly limited, can from commercially available product, suit to select to use.

As the pigment dyestuff that presents purple, C.I. pigment violet 1 (rhodamine B), C.I. pigment violet 2 (rhodamine 3B), C.I. pigment violet 3 (methyl violet color lake), C.I. pigment violet 3: 1 (methyl violet color lake), C.I. pigment violet 3: 3 (methyl violet color lakes), C.I. pigment violet 5:1 (alizarin violet), C.I. pigment violet 13 (ultramarine is red), C.I. pigment violet 17 (naphthols AS), C.I. pigment Violet 23 (dioxazine violet), C.I. pigment violet 25 (naphthols AS), C.I. pigment violet 29 (perylene purples), C.I. pigment violet 31 (isoviolanthrone), C.I. pigment violet 32 (the red HF3R of benzimidazolone wine), C.I. pigment violet 36 (thioindigo), C.I. pigment violet 37 (dioxazine violets), C.I. pigment violet 42 (quinacridone violet B), C.I. pigment violet 50 (naphthols AS) etc. can be used as commercially available product and obtains.

Wherein, disperse the viewpoint of the stability of thing to consider from color reproduction, photostabilization and pigment dyestuff, as the pigment dyestuff that presents purple, preferred C.I. pigment Violet 23, C.I. pigment violet 32, C.I. pigment violet 37 and C.I. pigment violet 39, special preferred pigments purple 23, pigment violet 37.

As presenting orange pigment dyestuff, C.I. pigment orange 1 (organic yellow 3R), C.I. pigment orange 2 (adjacent nitro orange), C.I. pigment orange 3 (Beta Naphthol 99MIN), C.I. pigment orange 4 (naphthols AS), C.I. pigment orange 5 (Beta Naphthol 99MIN), C.I. pigment Orange 13 (pyrazolone orange G), C.I. pigment orange 15 (tetrazo orange), C.I. pigment orange 16 (methyl oxyaniline orange), C.I. pigment orange 17 (orange shallow lake, Persian), C.I. pigment orange 19 (naphthalene yellow color lake), C.I. pigment orange 24 (naphthol orange Y), C.I. pigment orange 31 (condensation azo orange), C.I. pigment orange 34 (pyrazolone orange), C.I. pigment orange 36 (benzimidazolone orange HL), C.I. pigment orange 38 (naphthol orange), C.I. pigment orange 40 (pyranthrone orange), C.I. pigment orange 43 (purple cyclic ketones orange), C.I. pigment orange 46 (ethyl red color lake C), C.I. pigment orange 48 (quinacridone quinone), C.I. pigment orange 49 (quinacridone quinone), C.I. pigment orange 51 (pyranthrone orange), C.I. pigment orange 60 (imidazolone orange HGL), C.I. pigment orange 61 (isoindolinone orange), C.I. pigment orange 62 (benzimidazolone orange H5G), C.I. pigment orange 64 (benzimidazolone), C.I. pigment orange 65 (azomethine orange), C.I. pigment orange 66 (isoindoline orange), C.I. pigment orange 67 (pyrazolo quinolinone orange), C.I. pigment orange 68 (azomethine orange), C.I. pigment orange 69 (isoindolinone orange), C.I. pigment orange 71 (diketopyrrolopyrrolecocrystals orange), C.I. pigment orange 72 (imidazolone orange H4GL), C.I. pigment orange 73 (diketopyrrolopyrrolecocrystals orange), C.I. pigment orange 74 (naphthol orange 2RLD), C.I. pigment orange 81 (diketopyrrolopyrrolecocrystals orange) etc. can be used as commercially available product and obtains.

Wherein, disperse the viewpoint of the stability of thing to consider from color reproduction, photostabilization and pigment dyestuff, as presenting orange pigment dyestuff, can list C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 43, C.I. pigment orange 71, preferred especially C.I. pigment orange 36.

As presenting green pigment dyestuff, C.I. Pigment green 1 (bright green shallow lake), C.I. Pigment green 4 (malachite green color lake), C.I. pigment Green 7 (phthalocyanine green), C.I. Pigment green 8 (pigment green B), C.I. Pigment green 10 (nickel azophosphine), C.I. pigment green 36 (bromination phthalocyanine green) etc. can be used as commercially available product and obtain.

Wherein, disperse the viewpoint of the stability of thing to consider from color reproduction, photostabilization and pigment dyestuff, as presenting green pigment dyestuff, preferred C.I. pigment Green 7, C.I. pigment green 36, C.I. Pigment green 37, preferred especially C.I. pigment Green 7.

In addition, consider that from viewpoint preferred pigment dyestuff is a dioxazine type compound especially to the good dispersity of (B) described later composition (from the monomeric macromolecular compound of formula (1-1) expression).As dioxazine type compound, can list following formula (A) expression De dioxazine compound.

Wherein, R ¹～R ¹⁰Represent hydrogen atom, halogen atom (fluorine atom, chlorine atom, bromine atoms, iodine atom) or 1 valency group respectively independently.In addition, R ¹～R ¹⁰In any can be more than two in conjunction with forming ring structure, this ring structure can also have substituting group.

As 1 valency group; can list for example amino, substituted-amino, substituted carbonyl, hydroxyl, substituted oxy, thiol group, thioether group, silyl, nitro, cyano group, alkyl, alkenyl, aryl, heterocyclic radical, sulfo group, substituted sulphonyl, sulfonic acid foundation, substituted sulfinyl, phosphono, replacement phosphono, phosphonic acids foundation, replacement phosphonic acids foundation etc., in the time can introducing substituting group, can also have substituting group again.

As R ¹～R ¹⁰In alkyl, can list carbonatoms and be 1～20 straight chain shape, chain or cyclic alkyl.Wherein, more preferably carbonatoms is that 1～12 straight catenate alkyl, carbonatoms are that 3～12 catenate alkyl and carbonatoms are 5～10 cyclic alkyl.As its object lesson, can list for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, isopentyl, neo-pentyl, 1-methyl butyl, isohexyl, 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl, 2-norborneol alkyl.

Work as R ¹～R ¹⁰In alkyl when having substituting group (, when being substituted alkyl), moieties as substituted alkyl, can list on above-mentioned carbonatoms is 1～20 alkyl and remove the group that any one hydrogen atom forms the organic residue of divalence, also identical for the scope of preferred carbonatoms with abovementioned alkyl.

As R ¹～R ¹⁰Preferred object lesson when being substituted alkyl; can list chloromethyl; brooethyl; the 2-chloroethyl; trifluoromethyl; methoxymethyl; the methoxycarbonyl methyl; the isopropoxy methyl; butoxymethyl; the sec-butoxy butyl; methoxyethoxyethyl; the allyloxy methyl; phenoxymethyl; acetoxy-methyl; methylthiomethyl; toluene sulfenyl methyl; pyridylmethyl; the tetramethyl piperidine ylmethyl; N-ethanoyl tetramethyl piperidine ylmethyl; the trimethyl silyl methyl; methoxy ethyl; the ethylamino ethyl; the diethylamino propyl group; the morpholino propyl group; the benzoyloxy methyl; N-cyclohexyl carboxyamide base oxygen base ethyl; N-phenyl amino formyl radical oxygen base ethyl; the acetylamino ethyl; N-methyl benzoyl aminopropyl; the 2-oxoethyl; the 2-oxopropyl; the carboxyl propyl group; the methoxycarbonyl ethyl; the allyloxy carbonyl butyl; chloro phenyloxycarbonyl methyl; the carbamyl ylmethyl; N-methylamino formyl radical ethyl; N; N-dipropyl carbamyl ylmethyl; N-(p-methoxy-phenyl) formamyl ethyl; N-methyl-N-(sulfo group phenyl) carbamyl ylmethyl; the sulfo group butyl; sulfonic acid foundation butyl; the sulfamyl butyl; N-ethyl sulfamyl methyl; N, N-dipropyl sulfamyl propyl group; N-tolyl sulfamyl propyl group; N-methyl-N-(phosphono phenyl) sulfamyl octyl group; the phosphono butyl; the phosphonic acid ester hexyl; diethyl phosphonic acids butyl; phenylbenzene phosphonic acids propyl group; the methyl-phosphorous acid butyl; methyl-phosphorous acid foundation butyl; tolylphosphine acyl group hexyl; tolylphosphine acid group base hexyl; phosphorus acyloxy propyl group; the phosphonato butyl; benzyl; styroyl; α-Jia Jibianji; 1-methyl isophthalic acid-styroyl; to methyl-benzyl; cinnamyl; allyl group; 1-propenyl methyl; crotyl; the 2-methacrylic; 2-methacrylic ylmethyl; 2-propynyl; the 2-butyne base; 3-butynyl etc.

As being incorporated into R ¹～R ¹⁰In alkyl on substituting group, the substituting group of in the explanation of above-mentioned substituted alkyl, putting down in writing, also can list the following illustrative 1 valency substituting group that constitutes by non-metallic atom.As comprising above-mentioned substituent preferred example, can list:

Halogen atom (F,-Br,-Cl,-I), hydroxyl, alkoxyl group, aryloxy, sulfydryl, alkylthio, arylthio, the alkyl disulfide group, the aryl disulfide group, amino, the N-alkylamino, N, the N-dialkyl amido, the N-arylamino, N, the N-ammonia diaryl base, N-alkyl-N-arylamino, acyloxy, formamyl oxygen base, N-alkyl-carbamoyl oxygen base, N-aryl-amino-carbonyl oxygen base, N, N-dialkyl amido formyl radical oxygen base, N, N-ammonia diaryl base formyl radical oxygen base, N-alkyl-N-aryl-amino-carbonyl oxygen base, alkyl sulfide oxygen base, aryl sulphur oxygen base, the acyl sulfenyl, acyl amino, N-alkyl acyl amino, N-aryl-acyl amino, urea groups, N '-alkyl urea groups, N ', N '-dialkyl group urea groups, N '-aryl-ureido, N ', N '-diaryl urea groups, N '-alkyl-N '-aryl-ureido, N-alkyl urea groups, the N-aryl-ureido, N '-alkyl-N-alkyl urea groups, N '-alkyl-N-aryl-ureido, N ', N '-dialkyl group-N-alkyl urea groups, N ', N '-dialkyl group-N-aryl-ureido, N '-aryl-N-alkyl urea groups, N '-aryl-N-aryl-ureido, N ', N '-diaryl-N-alkyl urea groups, N ', N '-diaryl-N-aryl-ureido, N '-alkyl-N '-aryl-N-alkyl urea groups, N '-alkyl-N '-aryl-N-aryl-ureido;

Alkoxycarbonyl amino; aryloxycarbonyl amino; N-alkyl-N-alkoxycarbonyl amino; N-alkyl-N-aryloxycarbonyl amino; N-aryl-N-alkoxycarbonyl amino; N-aryl-N-aryloxycarbonyl amino; formyl radical; acyl group; carboxyl; alkoxy carbonyl; aryloxycarbonyl; formamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formyl radical; the N-aryl-amino-carbonyl; N, N-ammonia diaryl base formyl radical; N-alkyl-N-aryl-amino-carbonyl; alkyl sulphinyl; aryl sulfonyl kia; alkyl sulphonyl; aryl sulfonyl; sulfo group (SO ₃H) and the conjugation base (below; be called the sulfonic acid foundation), alkoxyl group alkylsulfonyl, aryloxy sulfonyl, sulfinamoyl (sulfinamoyl), N-alkyl sulfinamoyl, N; N-dialkyl amino sulfinyl, N-aryl sulfinamoyl, N; N-ammonia diaryl sulfinyl, N-alkyl-N-aryl sulfinamoyl, sulfamyl, N-alkylsulfamoyl group, N; N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N, N-ammonia diaryl alkylsulfonyl, N-alkyl-N-ammonia aryl sulfonyl,

Phosphono (PO ₃H ₂) and the conjugation base (below, be called the phosphonic acids foundation.), dialkyl phosphine acyl group (PO ₃(alkyl) ₂) (alkyl=alkyl, below so same), diaryl phosphono (PO ₃(aryl) ₂) (aryl=aryl, below so same), alkylaryl phosphono (PO ₃(alkyl) (aryl)), monoalkyl phosphono (PO ₃H (alkyl)) and the conjugation base (below, be called the alkyl phosphonic acid foundation.), single aryl phosphine acyl group (PO ₃H (aryl)) and the conjugation base (below, be called the arylphosphonic acid foundation.), phosphorus acyloxy (OPO ₃H ₂) and conjugation base (below, be called the phosphorus acyloxy), dialkyl group phosphorus acyloxy (OPO ₃(alkyl) ₂), diaryl phosphorus acyloxy (OPO ₃(aryl) ₂), alkylaryl phosphorus acyloxy (OPO ₃(alkyl) (aryl)), monoalkyl phosphorus acyloxy (OPO ₃H (alkyl)) and the conjugation base (below, be called alkyl phosphorus acyloxy.), single aryl phosphorus acyloxy (OPO ₃H (aryl)) and the conjugation base (below, be called aryl phosphorus acyloxy.), cyano group, nitro, aryl, alkenyl, alkynyl, heterocyclic radical, silyl etc.

As being incorporated into R ¹～R ¹⁰In alkyl on substituting group in the object lesson of moieties, with above-mentioned R ¹～R ¹⁰For the situation of substituted alkyl is identical, preferred range is also identical.

In addition, as being incorporated into R ¹～R ¹⁰In alkyl on substituting group in the object lesson of aryl moiety, can list phenyl; xenyl; naphthyl; tolyl; xylyl; the sym-trimethylbenzene base; cumenyl; chloro-phenyl-; bromophenyl; chloromethyl phenyl; hydroxy phenyl; p-methoxy-phenyl; ethoxyl phenenyl; Phenoxyphenyl; the acetoxyl group phenyl; the benzoyloxy phenyl; the methylthio group phenyl; the thiophenyl phenyl; the methylamino phenyl; dimethylaminophenyl; the acetylamino phenyl; carboxyl phenyl; the methoxycarbonyl phenyl; the ethoxyl phenenyl carbonyl; the phenyloxycarbonyl phenyl; N-phenyl amino formyl radical phenyl; cyano-phenyl; the sulfo group phenyl; sulfonic acid foundation phenyl; the phosphono phenyl; phosphonic acids foundation phenyl etc.

As R ¹～R ¹⁰In alkenyl, can list carbonatoms and be 2～20 alkenyl.Wherein, preferred carbonatoms is 2～10 alkenyl, and more preferably carbonatoms is 2～8 alkenyl.Alkenyl also can have substituting group again.As the substituting group that can introduce, can list for example halogen atom, alkyl, substituted alkyl, aryl and substituted aryl, preferred halogen atom, carbonatoms are 1～10 straight chain shape, a chain, cyclic alkyl.As the object lesson of alkenyl, can list for example vinyl, 1-propenyl, 1-butylene base, cinnamyl, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-methyl isophthalic acid-propenyl, 2-methyl isophthalic acid-propenyl, 2-methyl-1-butene thiazolinyl, 2-phenyl-1-vinyl, 2-chloro-1-vinyl etc.

As R ¹～R ¹⁰In alkynyl, can list carbonatoms and be 2～20 alkynyl.Wherein, preferred carbonatoms is 2～10 alkynyl, and more preferably carbonatoms is 2～8 alkynyl.As its object lesson, can list ethynyl, 1-proyl, ethyl acetylene base, phenylacetylene base, trimethyl silyl ethynyl etc.

As R ¹～R ¹⁰In aryl, can list that phenyl ring, 2～3 phenyl ring form condensed ring and the group that forms, phenyl ring and five yuan of unsaturated rings form condensed ring and the group that forms.As object lesson, can list phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, fluorenyl, wherein, more preferably phenyl, naphthyl.

In addition, R ¹～R ¹⁰In aryl can on the carbon atom that forms ring, have substituting group, as such substituting group, can list the 1 valency substituting group that constitutes by non-metallic atom.Substituent preferred example as introducing can list the group of being put down in writing in the substituent explanation in above-mentioned alkyl, substituted alkyl and substituted alkyl.

As R ¹～R ¹⁰In heterocyclic radical, the heterocyclic radical of preferred 3～8 yuan of rings more preferably contains the heterocyclic radical of 3～6 yuan of rings of nitrogen-atoms, Sauerstoffatom, sulphur atom, further preferably contains the heterocyclic radical of 5～6 yuan of rings of nitrogen-atoms, Sauerstoffatom, sulphur atom.Specifically, can list pyrroles's cyclic group, furan nucleus, the thiophene cyclic group, the benzopyrrole cyclic group, the cumarone cyclic group, the thionaphthene cyclic group, pyrazoles cyclic group; isoxazole cyclic group, the isothiazole cyclic group, the indazole cyclic group, the benzoisoxazole cyclic group, the benzisothiazole cyclic group, imidazoles cyclic group; oxazole cyclic group, the thiazole cyclic group, benzoglyoxaline cyclic group; benzoxazole cyclic group, the benzothiazole cyclic group, the pyridine cyclic group, the quinoline cyclic group, the isoquinoline 99.9 cyclic group, the pyridazine cyclic group, the pyrimidine cyclic group, the pyrazine cyclic group, the phthalazines cyclic group, quinazoline cyclic group quinoxaline cyclic group, the aziridine cyclic group, the phenanthridines cyclic group, the carbazole cyclic group, the purine cyclic group, the pyrans cyclic group, the piperidines cyclic group, the piperazine cyclic group, the morpholine cyclic group, the indoles cyclic group, the indolizine cyclic group, the chromene cyclic group, the cinnoline cyclic group, the acridine cyclic group, the phenothiazine cyclic group, the tetrazolium cyclic group, triazine cyclic group etc.

In addition, R ¹～R ¹⁰In heterocyclic radical can have substituting group at the carbonatoms that forms ring, as such substituting group, can list the 1 valency substituting group that constitutes by non-metallic atom.Substituent preferred example as introducing can list the group of being put down in writing in the substituent explanation in above-mentioned alkyl, substituted alkyl and substituted alkyl.

As R ¹～R ¹⁰In silyl, can have substituting group, preferred carbonatoms is 0～30 silyl, more preferably carbonatoms is 3～20 silyl, further preferred carbonatoms is 3～10 silyl.As its object lesson, can list trimethyl silyl, triethylsilyl, tripropyl silyl, triisopropyl silyl, cyclohexyl dimetylsilyl, dimethyl vinyl silyl etc.

As R ¹～R ¹⁰In thiol group, can have substituting group, preferred carbonatoms is 0～30 thiol group, more preferably carbonatoms is 3～20 thiol group, further preferred carbonatoms is 1～10 thiol group.As its object lesson, can list mercapto methyl, mercaptoethyl, 4-sulfydryl cyclohexyl, 4-sulfydryl phenyl etc.

As R ¹～R ¹⁰In thioether group, can have substituting group, preferred carbonatoms is 0～30 thioether group, more preferably carbonatoms is 3～20 thioether group, further preferred carbonatoms is 1～10 thioether group.

As its object lesson, can list arylthios such as alkylthio, thiophenyl such as methyl sulfenyl, ethyl sulfenyl, cyclohexyl sulfenyl etc.

As R ¹～R ¹⁰In halogen atom, can list fluorine atom, bromine atoms, chlorine atom, iodine atom, wherein, preferred chlorine atom and bromine atoms.

As R ¹～R ¹⁰In substituted oxy (R ⁰⁶O-), R ⁰⁶Can use the group that constitutes by the monovalence nonmetallic atom group except hydrogen atom.As preferred substituted oxy, can list alkoxyl group, aryloxy, acyloxy, carbamoyloxy, N-alkyl carbamoyloxy base, N-arylamino methanoyl, N, N-dialkyl amido methanoyl, N, N-ammonia diaryl base methanoyl, N-alkyl-N-arylamino methanoyl, alkyl sulfide oxygen base, aryl sulphur oxygen base, phosphonato and phosphonate radical close the oxygen base.As alkyl in these and aryl, can list as above-mentioned alkyl, substituted alkyl and aryl, the cited group of substituted aryl.In addition, as the acyl group (R in acyloxy ⁰⁷CO-), R ⁰⁷Can list alkyl, substituted alkyl, aryl and the substituted aryl enumerated as example formerly.In these substituting groups, more preferably alkoxyl group, aryloxy, acyloxy and aryl sulphur oxygen base.Object lesson as preferred substituted oxy, can list methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, the benzene oxyethyl group, the carboxyl oxyethyl group, the methoxycarbonyl oxyethyl group, the ethoxycarbonyl oxyethyl group, methoxy ethoxy, the phenoxy group oxyethyl group, the methoxy ethoxy oxyethyl group, ethoxy ethoxy ethoxy, the morpholino oxyethyl group, the morpholino propoxy-, the allyloxy ethoxy ethoxy, phenoxy group, tolyloxy, xylyloxy, 2,4,6-front three phenoxy group, cumene oxygen base, the methoxyl group phenoxy group, ethoxy phenoxy, chlorophenoxy, the bromine phenoxy group, acetoxyl group, benzoyloxy, naphthyloxy, the phenyl sulfonyloxy, phosphonato and phosphonate radical close the oxygen base.

R ¹～R ¹⁰In amino also can be the substituted-amino that contains amide group.As the substituted-amino (R that contains amide group ⁰⁸NH-, (R ⁰⁹) (R ⁰¹⁰) N-), R ⁰⁸, R ⁰⁹, R ⁰¹⁰Can use the group that constitutes by the monovalence nonmetallic atom group except hydrogen atom.Preferred example as substituted-amino, can list the N-alkylamino, N, the N-dialkyl amido, the N-arylamino, the N-arylamino, N, the N-ammonia diaryl base, N-alkyl-N-arylamino, amido, the N-alkyl amido, N-aryl amido, urea groups, N '-alkyl urea groups, N ', N '-dialkyl group urea groups, N '-aryl-ureido, N ', N '-diaryl urea groups, N '-alkyl-N '-aryl-ureido, N-alkyl urea groups, the N-aryl-ureido, N '-alkyl-N-alkyl urea groups, N '-alkyl-N-aryl-ureido, N ', N '-dialkyl group-N-alkyl urea groups, N ', N '-dialkyl group-N-aryl-ureido, N '-aryl-N-alkyl urea groups, N '-aryl-N-aryl-ureido, N ', N '-diaryl-N-alkyl urea groups, N ', N '-diaryl-N-aryl-ureido, N '-alkyl-N '-aryl-N-alkyl urea groups, N '-alkyl-N '-aryl-N-aryl-ureido, alkoxycarbonyl amido, aryloxy carbonyl amino, N-alkyl-N-alkoxycarbonyl amido, N-alkyl-N-aryloxy carbonyl amino, N-aryl-N-alkoxycarbonyl amido and N-aryl-N-aryloxy carbonyl amino.As alkyl in these and aryl, can list as above-mentioned alkyl, substituted alkyl and aryl, the cited group of substituted aryl the acyl group (R in acyl amino, N-alkyl acyl amino, the N-aryl-acyl amino ⁰⁷CO-) R ⁰⁷As mentioned above.Wherein,, can list N-alkylamino, N, N-dialkyl amido, N-arylamino and amido as preferred group.As the object lesson of preferred substituted-amino, can list methylamino, ethylamino, diethylamino, morpholino base, piperidyl, pyrrolidyl (pyrrolidino), phenyl amino, benzamido and kharophen.

As R ¹～R ¹⁰In substituted sulphonyl (R ⁰¹¹-SO ₂-), can use by R ⁰¹¹Be the group that constitutes by the monovalence nonmetallic atom group.As preferred example, can list alkyl sulphonyl, aryl sulfonyl, replacement or unsubstituted sulfamyl.As alkyl in these and aryl, can list as above-mentioned alkyl, substituted alkyl and aryl, the cited group of substituted aryl.Object lesson as such substituted sulphonyl; can list butyl alkylsulfonyl, phenyl sulfonyl, chloro-phenyl-alkylsulfonyl, sulfamyl, N-alkylsulfamoyl group, N, N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl etc.

As R ¹～R ¹⁰In sulfonic acid foundation (SO ₃ ^-) as mentioned above, refer to sulfo group (SO ₃The anion-radicals of conjugate base H).Usually preferably use together with counter cation mutually.As this phase counter cation, can list common known positively charged ion, promptly various types of (ammonium class, sulfonium class, class, iodine class and azines etc.) and metal ion class (Na ⁺, K ⁺, Ca ²⁺, Zn ²⁺Deng).

As R ¹～R ¹⁰In substituted carbonyl (R ⁰¹³-CO-), can use the group that constitutes by the monovalence nonmetallic atom group.Preferred example as substituted carbonyl; can list formyl radical, acyl group, carboxyl, carbalkoxy, aryloxy carbonyl, formamyl, N-alkyl-carbamoyl, N; N-dialkyl amido formyl radical, N-aryl-amino-carbonyl, N, N-ammonia diaryl base formyl radical and N-alkyl-N-aryl-amino-carbonyl.As alkyl in these and aryl, can list as above-mentioned alkyl, substituted alkyl and aryl, the cited group of substituted aryl.Wherein, as preferred substituted carbonyl; can list formyl radical, acyl group, carboxyl, carbalkoxy, aryloxy carbonyl, formamyl, N-alkyl-carbamoyl, N; N-dialkyl amido formyl radical and N-aryl-amino-carbonyl; as preferred substituted carbonyl, can list formyl radical, acyl group, carbalkoxy and aryloxy carbonyl.Object lesson as preferred substituted carbonyl; can list formyl radical, ethanoyl, benzoyl, carboxyl, methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl, dimethylaminophenyl vinyl carbonyl, methoxycarbonyl methoxycarbonyl, N-methylamino formyl radical, N-phenyl amino formyl radical, N, N-diethylamino formyl radical and morpholino carbonyl.

As R ¹～R ¹⁰In substituted sulfinyl (R ⁰¹⁴-SO-), R ⁰¹⁴Can use the group that constitutes by the monovalence nonmetallic atom group.As preferred example; can list alkyl sulphinyl, aryl sulfonyl kia, sulfinamoyl, N-alkyl sulfinamoyl, N; N-dialkyl amino sulfinyl, N-aryl sulfinamoyl, N, N-ammonia diaryl sulfinyl and N-alkyl-N-aryl sulfinamoyl.As alkyl in these and aryl, can list as above-mentioned alkyl, substituted alkyl and aryl, the cited group of substituted aryl.Wherein, can list alkyl sulphinyl, aryl sulfonyl kia as preferred example.As the object lesson of such substituted sulfinyl, can list hexyl sulfinyl, benzyl sulfinyl and tolyl sulfinyl.

R ¹～R ¹⁰In the replacement phosphono be meant that one or two hydroxyl on the phosphono is replaced by other organic oxo base and the group that forms; as preferred example, can list dialkyl phosphine acyl group, diaryl phosphono, alkylaryl phosphono, monoalkyl phosphono and single aryl phosphine acyl group.In these groups, more preferably dialkyl phosphine acyl group and diaryl phosphono.As such object lesson, can list diethyl phosphonyl, dibutyl phosphono, diphenylphosphine acyl group etc.

R ¹～R ¹⁰In phosphonic acids foundation (PO ₃H ^-,-PO ₃ ^2-) be meant and come from phosphono (PO ₃H ₂) one-level or secondary acid dissociative conjugate base anion-radicals.Usually preferably use together with counter cation mutually.As this phase counter cation, can list known those positively charged ions usually, promptly various types of (ammonium class, sulfonium class, class, iodine class and azines etc.) and metal ion class (Na ⁺, K ⁺, Ca ²⁺, Zn ²⁺Deng).

R ¹～R ¹⁰In replacement phosphonic acids foundation be in above-mentioned replacement phosphono, hydroxyl to be replaced into the conjugate base anion-radicals that an organic oxo base forms, as object lesson, can list above-mentioned monoalkyl phosphono (PO ₃H (alkyl)) and single aryl phosphine acyl group (PO ₃H (aryl)) conjugation base.

In addition, R ¹～R ¹⁰Can also interosculate respectively, form phenyl ring, heterocyclic condensed ring with their bonded carbon atoms.

R ¹～R ¹⁰Preferred version be listed below.

In the formula, R ¹～R ¹⁰Represent hydrogen atom, halogen atom (chlorine atom, bromine atoms) or 1 valency group respectively independently.In addition, R ¹～R ¹⁰In any can be more than two in conjunction with forming ring structure, this ring structure can also have substituting group again.

As 1 valency group; can list for example amino, substituted-amino, substituted carbonyl, hydroxyl, substituted oxy, thiol group, thioether group, silyl, nitro, cyano group, alkyl, alkenyl, aryl, heterocyclic radical, substituted sulphonyl, sulfonic acid foundation, substituted sulfinyl, replacement phosphono, phosphonic acids foundation, replacement phosphonic acids foundation etc., in the time can introducing substituting group, can also have substituting group again.

As R ¹～R ¹⁰In alkyl, can list carbonatoms and be 1～10 straight chain shape, chain and cyclic alkyl.Wherein, more preferably carbonatoms is that 1～6 straight catenate alkyl, carbonatoms are that 3～6 catenate alkyl and carbonatoms are 5～10 cyclic alkyl.As this object lesson, can list for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, isopentyl, neo-pentyl, 1-methyl butyl, isohexyl, cyclohexyl, cyclopentyl and 2-norborneol alkyl.

Work as R ¹～R ¹⁰In alkyl when having substituting group (, when being substituted alkyl), moieties as substituted alkyl, can list on above-mentioned carbonatoms is 1～10 alkyl and remove any one hydrogen atom, form the group of the organic residue of divalence, also identical for the scope of preferred carbonatoms with abovementioned alkyl.

As R ¹～R ¹⁰Preferred object lesson when being substituted alkyl; can list brooethyl; the 2-chloroethyl; trifluoromethyl; methoxymethyl; the methoxycarbonyl methyl; butoxymethyl; the sec-butoxy butyl; methoxyethoxyethyl; the allyloxy methyl; phenoxymethyl; methylthiomethyl; toluene sulfenyl methyl; pyridylmethyl; the trimethyl silyl methyl; methoxy ethyl; the ethylamino ethyl; the diethylamino propyl group; the benzoyloxy methyl; the acetylamino ethyl; N-methyl benzoyl aminopropyl; the 2-oxoethyl; the methoxycarbonyl ethyl; the allyloxy carbonyl butyl; chloro phenyloxycarbonyl methyl; N-methylamino formyl radical ethyl; N, N-dipropyl carbamyl ylmethyl; sulfonic acid foundation butyl; N-ethyl sulfamyl methyl; the diethyl phosphonyl butyl; benzyl; styroyl; α-Jia Jibianji; 1-methyl isophthalic acid-styroyl; to methyl-benzyl; cinnamyl; allyl group; crotyl; the 2-methacrylic; 2-propynyl; 3-butynyl etc.

As R ¹～R ¹⁰In preferred alkenyl, can list carbonatoms and be 2～8 alkenyl.Alkenyl also can have substituting group again.As the substituting group that can introduce, can list for example halogen atom, alkyl, substituted alkyl, aryl and substituted aryl, preferred halogen atom, carbonatoms are 1～6 straight chain shape, a chain, cyclic alkyl.As the object lesson of alkenyl, can list for example vinyl, 1-propenyl, 1-butylene base, 1-pentenyl, 1-hexenyl, 1-methyl isophthalic acid-propenyl, 2-methyl isophthalic acid-propenyl, 2-methyl-1-butene thiazolinyl, 2-phenyl-1-vinyl etc.

As R ¹～R ¹⁰In preferred alkynyl, can list carbonatoms and be 2～8 alkynyl.As its object lesson, can list ethynyl, 1-proyl, ethyl acetylene base etc.

As R ¹～R ¹⁰In preferred aryl groups, as object lesson more preferably phenyl, tolyl, chloro-phenyl-, p-methoxy-phenyl, naphthyl.

As R ¹～R ¹⁰In heterocyclic radical, preferably contain the heterocyclic radical of 5～6 yuan of rings of nitrogen-atoms, Sauerstoffatom, sulphur atom.Specifically, can list pyrroles's cyclic group, furan nucleus, thiophene cyclic group, benzopyrrole cyclic group, cumarone cyclic group, thionaphthene cyclic group, isoxazole cyclic group, isothiazole cyclic group, imidazoles cyclic group, oxazole cyclic group, thiazole cyclic group, benzoglyoxaline cyclic group, benzoxazole cyclic group, benzothiazole cyclic group, quinoline cyclic group, pyrimidine cyclic group, quinazoline cyclic group, quinoxaline cyclic group, carbazole cyclic group, piperidines cyclic group, piperazine cyclic group, morpholine cyclic group, indoles cyclic group, indolizine cyclic group, tetrazolium cyclic group, triazine cyclic group etc.More preferably pyrroles's cyclic group, benzopyrrole cyclic group, carbazole cyclic group, indoles cyclic group.

As R ¹～R ¹⁰In silyl, can have substituting group, preferred carbonatoms is 3～10 silyl.As its object lesson, can list trimethyl silyl, triethylsilyl, tripropyl silyl etc.

As R ¹～R ¹⁰In thiol group, can have substituting group, preferred carbonatoms is 1～10 thiol group.As its object lesson, can list mercapto methyl, mercaptoethyl, 4-sulfydryl cyclohexyl, 4-sulfydryl phenyl etc.

As R ¹～R ¹⁰In thioether group, can have substituting group, preferred carbonatoms is 1～10 thioether group.As its object lesson, can list arylthios such as alkylthio, thiophenyl such as methyl sulfenyl, ethyl sulfenyl, cyclohexyl sulfenyl etc.

As R ¹～R ¹⁰In halogen atom, preferred chlorine atom and bromine atoms.

As R ¹～R ¹⁰In the object lesson of preferred substituted oxy, can list methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, pentyloxy, hexyloxy, benzyloxy, allyloxy, benzene oxyethyl group, methoxy ethoxy, phenoxy group oxyethyl group, phenoxy group, tolyloxy, xylyloxy, sym-trimethylbenzene oxygen base, methoxyl group phenoxy group, chlorophenoxy, bromine phenoxy group etc.

R ¹～R ¹⁰In amino also can be the substituted-amino that contains amide group.As the object lesson of preferred substituted-amino, can list methylamino, ethylamino, diethylamino, morpholino base, piperidyl, pyrrolidyl (pyrrolidino), phenyl amino, benzamido and kharophen.

As R ¹～R ¹⁰In preferred substituted sulphonyl, can list alkyl sulphonyl, aryl sulfonyl.As the object lesson of such substituted sulphonyl, can list methyl sulphonyl, butyl alkylsulfonyl, phenyl sulfonyl, chloro-phenyl-alkylsulfonyl etc.

As R ¹～R ¹⁰In preferred substituted carbonyl can list formyl radical, acyl group, carboxyl, carbalkoxy and aryloxy carbonyl.As object lesson, can list formyl radical, ethanoyl, benzoyl, carboxyl, methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl etc.

As R ¹～R ¹⁰In preferred substituted sulfinyl, can list alkyl sulphinyl, aryl sulfonyl kia.As the object lesson of such substituted sulfinyl, can list hexyl sulfinyl, benzyl sulfinyl and tolyl sulfinyl etc.

As R ¹～R ¹⁰In the preferred phosphono that replaces, can list dialkyl phosphine acyl group, diaryl phosphono, alkylaryl phosphono, monoalkyl phosphono and single aryl phosphine acyl group.In these groups, more preferably dialkyl phosphine acyl group and diaryl phosphono.As such object lesson, can list diethyl phosphonyl, dibutyl phosphono, diphenylphosphine acyl group etc.

The pigment dyestuff of formula (A) expression is preferably the pigment dyestuff that presents purple.Below listed the pigment dyestuff that presents purple of formula (A) expression, but the present invention is not limited to this.

C.I. pigment Violet 23

C.I. pigment violet 37

When above-mentioned pigment dyestuff disperses, can suit to use for example various diverting devices such as ball mill, sand mill, masher, roller mill, aeropulverizer, clarifixator, pigment vibrator, kneader, agitator, Henschel mixer, colloidal mill, ultrasonic homogenizer, ball mill, wet type aeropulverizer.

Among the present invention, when above-mentioned pigment dyestuff disperses, especially preferably add (B) composition.

In addition, when pigment dyestuff disperses, can add as required be suitable for various pigment synergist as dispersing auxiliary.As the content of dispersing auxiliary in ink composite, preferably with respect to 100 weight part pigment dyestuffs be more than 1 weight part below 50 weight parts (in addition, among the present invention, " above 50 weight parts of 1 weight part are following " also is recited as " 1～50 weight part " or " 1 weight part～50 weight parts ".Below identical).

The dispersion medium that uses when pigment dyestuff is disperseed, be not particularly limited, can suit as required to select, for example, can be low-molecular-weight active radiation-curable compound as dispersion medium, also can be solvent as dispersion medium.But ink composite of the present invention is the ink composite of radiation-curing type, because ink composite makes its curing after using on the printing medium, so preferably do not contain solvent, is solvent-free.This is because residual when solvent is arranged in the solidified ink image, the solvent resistance deterioration, and residual solvent is easy to produce the problem of VOC (volatile organic compounds).Therefore, use active radiation-curable compound, wherein, consider, preferably select the minimum polymerizable compound of viscosity from the viewpoint that improves the processing that disperses adaptability and ink composite as above-mentioned dispersion medium.

That is, among the present invention, preferred (B) composition that uses is as dispersion agent, and (A) composition (presenting at least a of orange, purple or green pigment dyestuff) is scattered in the active radiation-curable compound, obtains pigment dyestuff and disperses thing.

Median size as pigment dyestuff is not particularly limited, and can suit as required to select, because trickle more color developing is excellent more, so be preferably about 0.01～0.4 μ m, more preferably 0.02～0.2 μ m.In addition, the maximum particle diameter of pigment dyestuff is preferably below the 3 μ m, more preferably below the 1 μ m.The particle diameter of pigment dyestuff can wait according to the setting of the selection of pigment dyestuff, dispersion agent, dispersion medium, dispersion condition, filtration condition and adjust, particle diameter by the control pigment dyestuff, the obstruction of nozzle be can suppress, the storage stability of ink composite, the transparency and the curing sensitivity of ink composite kept.

Among the present invention,,, also can form even and stable ink composite even when having used atomic pigment dyestuff owing to contain (B) composition of dispersiveness, excellent in stability.In addition,, also can obtain good dispersiveness, obtain the ink composite of color reproduction excellence even when using in the past dispersion agent can not obtain enough dispersed De dioxazine type compound pigment dyestuffs.

In addition, the particle diameter of pigment dyestuff in ink composite can be measured with known measuring method.Can measure with centrifugation light transmission method, X line penetrant method, laser diffraction, scattering method, dynamic light scattering method specifically.

As the content of pigment dyestuff in ink composite, be preferably 1～20 weight %, more preferably 2～10 weight %.

＜(B) from the monomeric macromolecular compound of formula (1-1) expression, from the monomeric macromolecular compound of formula (2-1) expression and the polymkeric substance of formula (3-1) expression

Ink composition for ink jet of the present invention contains at least a (below be also referred to as (B) composition) in the polymkeric substance of the monomeric macromolecular compound that is selected from the monomeric macromolecular compound that comes from formula (1-1) expression, formula (2-1) expression and formula (3-1) expression.Below, to describing from the monomeric macromolecular compound of formula (1-1) expression, the polymkeric substance of representing from the monomeric macromolecular compound and the formula (3-1) of formula (2-1) expression.

＜from the monomeric macromolecular compound of formula (1-1) expression 〉

As the macromolecular compound of (B) composition that uses among the present invention can be the monomeric homopolymer of formula (1-1) expression, preferably can with the multipolymer of this monomer copolymerization, be more preferably the graft copolymer that describes in detail later.

Among the present invention, the monomeric macromolecular compound that comes from formula (1-1) expression uses as pigment dispersing agent or plays a part pigment dispersing agent, affinity height with above-mentioned (A) composition, adsorptivity to this (A) composition is good, in addition, owing to be macromolecular compound,, contain the dispersion stabilization excellence of the ink composite of the present invention of (B) composition according to the steric repulsion effect of macromolecular chain with specific repeated structural unit.Even when using in being difficult to stable dispersion De dioxazine type compound pigment dyestuff, (B) composition also can demonstrate good dispersiveness in the past.

(monomer that uses among the present invention)

The monomer that uses among the present invention is represented with following formula (1-1).

R in the＜formula (1-1) ¹

In the above-mentioned formula (1-1), R ¹Expression hydrogen atom or replacement or unsubstituted alkyl.The carbonatoms of alkyl is preferably 1～12, and more preferably 1～8, more preferably 1～4.As alkyl, can list for example methyl, ethyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl etc.

R in the＜formula (1-1) ²

R ²The expression alkylidene group, carbonatoms is preferably 1～12, and more preferably 1～8, more preferably 1～4.As alkylidene group, can list for example methylene radical, ethylidene, propylidene, trimethylene, tetramethylene.

W in the＜formula (1-1) 〉

W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.

X in the＜formula (1-1) 〉

X represents-CO-,-NHCO-,-OC (=O)-,-CH (OH) CH ₂-or-SO ₂-.

M, n in the＜formula (1-1) 〉

M, n are respectively 0 or 1 independently.

R in the＜formula (1-1) ³, R ⁴

R ³, R ⁴Expression monovalence substituting group.R ³And R ⁴Can interconnection formation ring texture.

Above-mentioned R ³, R ⁴The monovalence substituting group of expression is preferably alkyl, aryl, halogen atom, alkoxyl group, aryloxy, alkylthio, arylthio, alkoxy carbonyl, acyl amino, formamyl, cyano group, alkyl sulphonyl, aryl sulfonyl, acyl group, sulfamyl, more preferably halogen atom, alkyl, aryl, alkoxyl group, aryloxy, alkylthio, arylthio, acyl amino, sulfuryl amino.

Above-mentioned R ³, R ⁴The substituting group of expression can not be substituted yet can have substituting group; as the substituting group that can be incorporated on this substituting group, be preferably alkyl, aryl, halogen atom, alkoxyl group, aryloxy, alkoxy carbonyl, acyloxy, acyl amino, formamyl, cyano group, carboxyl, alkylsulfonyl, heterocycle residue.

Above-mentioned R ³, R ⁴It is 1～30 alkyl that the alkyl of expression is preferably total carbon atom number, and more preferably total carbon atom number is 1～20 alkyl.Specifically; be preferably methyl; ethyl; butyl; hexyl; octyl group; the 2-ethylhexyl; 3; 5; 5-trimethylammonium hexyl; dodecyl; octadecyl; benzyl; (4-ethoxyl phenenyl) methyl; N; N-diethylamino formyl radical methyl; N; N-dibutylamino formyl radical methyl; 1-(N; N-dibutylamino formyl radical) ethyl; the 2-methoxy ethyl; 1-methyl-2-phenoxy group ethyl; (4-chloro-phenyl-) methyl; (2; the 4-dichlorophenyl) methyl; ethyl more preferably; butyl; hexyl; benzyl; N; N-diethylamino formyl radical methyl; N; N-dibutylamino formyl radical methyl; 1-(N; N-dibutylamino formyl radical) ethyl; 1-methyl-2-phenoxy group ethyl; (4-chloro-phenyl-) methyl; (2,4 dichloro benzene base) methyl.

Above-mentioned R ³, R ⁴It is 6～30 aryl that the aryl of expression is preferably total carbon atom number, and more preferably total carbon atom number is 1～20 aryl.Specifically; be preferably phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 4-phenyl phenoxy group, 4-chloro-phenyl-, 2-p-methoxy-phenyl, 3-ethoxyl phenenyl, 4-butoxy phenyl, 2; 4-diethoxy phenyl, 2; 5-dibutoxy phenyl, 4-Phenoxyphenyl, naphthyl, 4-dibutylamino formyl radical phenyl, 4-dibutylamine alkylsulfonyl phenyl, more preferably phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 4-chloro-phenyl-, 2-p-methoxy-phenyl, 3-ethoxyl phenenyl, 4-butoxy phenyl.

Above-mentioned R ³, R ⁴The halogen atom of expression is preferably fluorine atom, chlorine atom, bromine atoms, iodine atom, more preferably fluorine atom, chlorine atom.

As above-mentioned R ³, R ⁴The alkoxyl group of expression is preferably total carbon atom number and is 1～30 alkoxyl group, and more preferably total carbon atom number is 1～20 alkoxyl group.As substituting group; be preferably methoxyl group, oxyethyl group, propoxy-, butoxy, hexyloxy, 2-ethyl hexyl oxy, 3; 5; 5-trimethylammonium hexyloxy, octyloxy, the last of the ten Heavenly stems oxygen base, 2-phenoxy group oxyethyl group, 2-(3; 5-di-t-butyl phenoxy group) oxyethyl group, dibutylamino formyl radical methoxyl group, n-Hexadecane oxygen base, octadecane oxygen base; more preferably methoxyl group, oxyethyl group, butoxy, hexyloxy, 2-ethyl hexyl oxy, 3; 5,5-trimethylammonium hexyloxy, 2-phenoxy group oxyethyl group, dibutylamino formyl radical methoxyl group.

As above-mentioned R ³, R ⁴The aryloxy of expression is preferably total carbon atom number and is 6～30 aryloxy, and more preferably total carbon atom number is 6～20 aryloxy.As substituting group; be preferably phenoxy group, tolyloxy, 4-chlorophenoxy, 4-ethanamide phenoxy group, 2-phenoxy butoxy base, 2-benzoyl-amido phenoxy group, 2; 5-dimethoxy-4 '-nitro-phenoxy, 3-octyloxy phenoxy group; more preferably phenoxy group, tolyloxy, 4-chlorophenoxy, 4-ethanamide phenoxy group, 2-phenoxy butoxy base, 2,5-dimethoxy-4 '-nitro-phenoxy.

As above-mentioned R ³, R ⁴The alkylthio of expression is preferably total carbon atom number and is 1～30 alkylthio, and more preferably total carbon atom number is 1～20 alkylthio.As substituting group; be preferably the methyl sulfenyl; the ethyl sulfenyl; the butyl sulfenyl; the hexyl sulfenyl; 2-ethylhexyl sulfenyl; 3; 5; 5-trimethylammonium hexyl sulfenyl; the octyl group sulfenyl; the decyl sulfenyl; 2-phenoxy group ethyl sulfenyl; 2-(3; 5-di-t-butyl phenoxy group) ethyl sulfenyl; dibutylamino formyl radical methyl sulfenyl; the hexadecyl sulfenyl; the octadecyl sulfenyl; methyl sulfenyl more preferably; the ethyl sulfenyl; the butyl sulfenyl; the hexyl sulfenyl; 2-ethylhexyl sulfenyl; 3; 5,5-trimethylammonium hexyl sulfenyl; 2-phenoxy group ethyl sulfenyl; dibutylamino formyl radical methyl sulfenyl.

As above-mentioned R ³, R ⁴The arylthio of expression is preferably total carbon atom number and is 6～30 arylthio, and more preferably total carbon atom number is 6～20 arylthio.As substituting group; be preferably phenyl sulfenyl, tolyl sulfenyl, 4-chloro-phenyl-sulfenyl, 4-ethanamide phenyl sulfenyl, 2-butoxy phenyl sulfenyl, 2-benzoyl-amido phenyl sulfenyl, 2; 5-dimethoxy-4 '-nitrophenyl sulfenyl, 3-octyloxyphenyl sulfenyl; more preferably phenyl sulfenyl, tolyl sulfenyl, 4-chloro-phenyl-sulfenyl, 4-ethanamide phenyl sulfenyl, 2-butoxy phenyl sulfenyl, 2,5-dimethoxy-4 '-nitrophenyl sulfenyl.

As above-mentioned R ³, R ⁴The alkoxy carbonyl of expression is preferably total carbon atom number and is 2～30 alkoxy carbonyl, and more preferably total carbon atom number is 2～20 alkoxy carbonyl.As substituting group, be preferably methoxycarbonyl, ethoxy carbonyl, butoxy carbonyl, phenyloxycarbonyl, (2-ethylhexyl) oxygen base carbonyl, hexyloxy carbonyl, carbonyl octyloxy, (4-p-methoxy-phenyl) oxygen base carbonyl, more preferably methoxycarbonyl, ethoxy carbonyl, butoxy carbonyl, phenyloxycarbonyl.

As above-mentioned R ³, R ⁴The acyl amino of expression is preferably total carbon atom number and is 1～30 acyl amino, and more preferably total carbon atom number is 1～20 acyl amino.As substituting group; be preferably formyl radical amino; acetylamino; butyryl radicals amino; lauroyl amino; benzoyl-amido; toluyl amino; the phenoxy group ethanoyl; (4-methoxyl group phenoxy group) ethanoyl; 2 '; 4 '-dichloro-benzoyl base amino; 2 '; 4 '-two tert-pentyl benzoyl-amidos; the ethanoyl methylamino; the benzoyl methylamino; the ethanoyl benzylamino; acetylamino more preferably; butyryl radicals amino; benzoyl-amido; toluyl amino; the phenoxy group ethanoyl; 2 ', 4 '-two tert-pentyl benzoyl-amidos; the ethanoyl methylamino; the benzoyl methylamino; the ethanoyl benzylamino.

As above-mentioned R ³, R ⁴The formamyl of expression, more preferably total carbon atom number is 1～30 formamyl, more preferably total carbon atom number is 1～20 formamyl.As substituting group; be preferably formamyl; N-phenyl amino formyl radical; N-butyl formamyl; N-octyl group formamyl; N; the N-formyl-dimethylamino; N; N-diethylamino formyl radical; N; N-dibutylamino formyl radical; N; N-dihexyl formamyl; N; N-diphenyl amino formyl radical; N-methyl-N-phenyl amino formyl radical; N-ethyl-N-phenyl amino formyl radical; N-methyl-N-tolyl formamyl; morpholino carbonyl; piperidino carbonyl; N; N-two (2-methoxy ethyl) formamyl; N-butyl formamyl more preferably; N-octyl group formamyl; N-phenyl amino formyl radical; N; N-diethylamino formyl radical; N, N-dibutylamino formyl radical; N-methyl-N-phenyl amino formyl radical.

As above-mentioned R ³, R ⁴The alkyl sulphonyl of expression is preferably total carbon atom number and is 1～30 alkyl sulphonyl, and more preferably total carbon atom number is 1～20 alkyl sulphonyl.As substituting group, be preferably methyl sulphonyl, ethylsulfonyl, butyl alkylsulfonyl, hexyl alkylsulfonyl, benzyl alkylsulfonyl, more preferably methyl sulphonyl, benzyl alkylsulfonyl.

As above-mentioned R ³, R ⁴The aryl sulfonyl of expression is preferably total carbon atom number and is 1～30 aryl sulfonyl, and more preferably total carbon atom number is 1～20 aryl sulfonyl.As substituting group, be preferably phenyl sulfonyl, 4-aminomethyl phenyl alkylsulfonyl, naphthyl alkylsulfonyl, 4-methoxyl group alkylsulfonyl, 4-chloro-phenyl-alkylsulfonyl, more preferably methyl sulphonyl, phenyl sulfonyl, 4-aminomethyl phenyl alkylsulfonyl.

As above-mentioned R ³, R ⁴The acyl group of expression is preferably total carbon atom number and is 1～30 acyl group, and more preferably total carbon atom number is 1～20 acyl group.As substituting group; be preferably formyl radical, ethanoyl, propionyl, valeryl, butyryl radicals, 4-phenoxy group butyryl radicals, benzoyl, (4-ethoxyl phenenyl) carbonyl, (2-butoxy phenyl) carbonyl, (4-chloro-phenyl-) carbonyl, more preferably formyl radical, ethanoyl, propionyl, valeryl, benzoyl, (4-chloro-phenyl-) carbonyl.

As above-mentioned R ³, R ⁴The sulfamyl of expression is preferably total carbon atom number and is 1～30 sulfamyl, and more preferably total carbon atom number is 1～20 sulfamyl.As substituting group; be preferably sulfamyl; N-phenyl sulfamoyl base; N; N-dimethylamino alkylsulfonyl; N; N-diethyl amino alkylsulfonyl; N; N-dibutylamine alkylsulfonyl; N; N-dihexyl sulfamyl; N; N-phenylbenzene sulfamyl; N-methyl-N-phenyl sulfamoyl base; N-ethyl-N-phenyl sulfamoyl base; N-methyl-N-tolyl sulfamyl; the morpholino alkylsulfonyl; the piperidyl alkylsulfonyl; N; N-two (2-methoxy ethyl) alkylsulfonyl; sulfamyl more preferably; N-phenyl sulfamoyl base; N; N-dibutylamine alkylsulfonyl; N, N-phenylbenzene sulfamyl; N-methyl-N-phenyl sulfamoyl base.

In addition, the monomer that uses among the present invention is preferably the monomer of following formula (1-2) expression.

R in the formula (1-2) ³, R ⁴Expression monovalence substituting group.R ³And R ⁴Can interconnection formation ring texture.The example of preferred substituted is identical with the situation of above-mentioned formula (1-1).

The preferred object lesson of compound as formula (1-1) or formula (1-2) expression is listed below.In addition, the present invention is not limited to this.

＜compound example 〉

(macromolecular compound)

The macromolecular compound that uses among the present invention is the polymkeric substance that contains from the copolymerization units of the polymerizable compound (monomer) of above-mentioned formula (1-1) or formula (1-2) expression.

Above-mentioned macromolecular compound preferably also contains the polyreactive oligomers that the has the ethylenic unsaturated double-bond endways graft copolymer as copolymerization units.

This have the polyreactive oligomers of ethylenic unsaturated double-bond endways owing to be the compound with regulation molecular weight, so be also referred to as macromonomer.

Above-mentioned polyreactive oligomers has can forming by the polymeric functional moieties of ethylenic unsaturated double-bond by the polymer chain part with at its end.Consider that from the viewpoint that obtains desirable graft copolymer this group with ethylenic unsaturated double-bond preferably only has at an end of polymer chain.Group as having the ethylenic unsaturated double-bond is preferably (methyl) acryl, vinyl, more preferably (methyl) acryl.

In addition, the number-average molecular weight (Mn) that this macromonomer preferably converts through polyethylene is 1,000～10,000 scope, more preferably 2,000～9,000 scope.

Above-mentioned polymer chain partly is preferably the homopolymer that formed by at least a monomer that is selected from (methyl) alkyl acrylate, vinylbenzene and derivative, vinyl cyanide, vinyl acetate and the divinyl or multipolymer or polyethylene oxide, poly(propylene oxide), polycaprolactone.

Above-mentioned polyreactive oligomers is preferably the oligopolymer of following formula (1-3) expression.

In the above-mentioned formula (1-3), R ¹¹And R ¹³Represent hydrogen atom or methyl, R respectively independently ¹²The expression carbonatoms is that (preferred carbonatoms is 2～4 alkylidene group for 1～12 alkylidene group, can have substituting group (for example hydroxyl), can also connect by ester bond, ehter bond, amido linkage etc.), Y represents phenyl, have phenyl that carbonatoms is 1～4 alkyl or-COOR ¹⁴(wherein, R ¹⁴The expression carbonatoms is that 1～6 alkyl, phenyl or carbonatoms are 7～10 arylalkyl), q is 20～200.Y be preferably phenyl or-COOR ¹⁴(wherein, R ¹⁴Be that carbonatoms is 1～12 alkyl).

As the preferred example of above-mentioned polyreactive oligomers (macromonomer), can list the polymkeric substance going up combination (methyl) acryl and form in the molecular end of poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate and poly-(methyl) isobutyl acrylate, polystyrene.This polyreactive oligomers that can obtain as market; can list a terminal methyl group acryl polystyrene oligopolymer (Mn=6; 000, trade(brand)name: AS-6, Toagosei Co., Ltd's system), a terminal methyl group acryl polymethyl methacrylate oligomer (Mn=6; 000, trade(brand)name: AA-6, Toagosei Co., Ltd's system) and positive butyl ester oligopolymer of terminal methyl group acryl polyacrylic acid (Mn=6,000, trade(brand)name: AB-6, Toagosei Co., Ltd's system).

Above-mentioned polyreactive oligomers is not only the polyreactive oligomers of above-mentioned formula (1-3) expression, also can be the polyreactive oligomers of following formula (1-4) expression.

In the above-mentioned formula (1-4), R ²¹Expression hydrogen atom or methyl, R ²²The expression carbonatoms is 1～8 alkylidene group.X ²¹Expression-OR ²³Perhaps-OCOR ²⁴R here ²³, R ²⁴Expression hydrogen atom, alkyl or aryl.N represents 2～200.

In the above-mentioned formula (1-4), R ²¹Expression hydrogen atom or methyl.R ²²The expression carbonatoms is 1～8 alkylidene group, wherein, is preferably carbonatoms and is 1～6 alkylidene group, and more preferably carbonatoms is 2～3 alkylidene group.X ²¹Expression-OR ²³Perhaps-OCOR ²⁴Here, R ²³Expression hydrogen atom, carbonatoms are 1～18 alkyl, phenyl or are the phenyl that 1～18 alkyl replaces by carbonatoms.R ²⁴The expression carbonatoms is 1～18 alkyl.In addition, n represents 2～200, is preferably 5～100, more preferably 10～100.

Polyreactive oligomers as above-mentioned formula (1-4) expression, can list for example polyoxyethylene glycol one (methyl) acrylate, polypropylene glycol one (methyl) acrylate, polyoxyethylene glycol polypropylene glycol one (methyl) acrylate, poly-1,4-butyleneglycol monomethyl acrylate etc., these can be commercially available products, also can be suitable synthetic.

The polymerizable monomer of above-mentioned formula (1-4) expression also can be used as commercially available product as mentioned above and obtains, as commercially available product, can list for example methoxy polyethylene glycol methacrylate-styrene polymer (trade(brand)name: NK esterM-40G, M-90G, M-230G (above these are Xin Zhong village chemical industry Co., Ltd. system); Trade(brand)name: BLENMER-PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (above these by Japan Oil Co's system)), polyoxyethylene glycol monomethyl acrylate (trade(brand)name: BLENMER-PE-90, PE-200, PE-350, Japan Oil Co's system), polypropylene glycol monomethyl acrylate (trade(brand)name: BLENMER-PP-500, PP-800, PP-1000, Japan Oil Co's system), polyoxyethylene glycol polypropylene glycol monomethyl acrylate (trade(brand)name: BLENMER-70PEP-370B, Japan Oil Co's system), polyoxyethylene glycol poly-1,4-butyleneglycol monomethyl acrylate (trade(brand)name: BLENMER-55PET-800, Japan Oil Co's system), polypropylene glycol poly-1,4-butyleneglycol monomethyl acrylate (trade(brand)name: BLENMER-NHK-5050, Japan Oil Co's system) etc.

Employed polymkeric substance can also be the multipolymer that forms with the monomer with nitrogen-atoms among the present invention.As monomer with nitrogen-atoms, can list for example N, N-dimethyl aminoethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylate, 1-(N, the N-dimethylamino)-1,1-dimethyl methyl (methyl) acrylate, N, N-dimethylamino hexyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N, N-diisopropylaminoethyl ethyl (methyl) acrylate, N, N-di-n-butyl amino-ethyl (methyl) acrylate, N, N-Di-Isobutyl amino-ethyl (methyl) acrylate, morpholino ethyl (methyl) acrylate, piperidyl ethyl (methyl) acrylate, 1-pyrrolidyl ethyl (methyl) acrylate, N, N-methyl-2-pyrrolinyl amino-ethyl (methyl) acrylate, and N, N-aminomethyl phenyl amino-ethyl (methyl) acrylate (more than be designated as (methyl) esters of acrylic acid); Dimethyl (methyl) acrylamide, diethyl (methyl) acrylamide, di-isopropyl (methyl) acrylamide, di-n-butyl (methyl) acrylamide, Di-Isobutyl (methyl) acrylamide, morpholino (methyl) acrylamide, piperidyl (methyl) acrylamide, N-methyl-2-pyrrolinyl (methyl) acrylamide and N, N-aminomethyl phenyl (methyl) acrylamide (more than be designated as (methyl) acrylic amide); 2-(N, the N-dimethylamino) ethyl (methyl) acrylamide, 2-(N, the N-diethylamino) ethyl (methyl) acrylamide, 3-(N, the N-diethylamino) propyl group (methyl) acrylamide, 3-(N, the N dimethylamino) propyl group (methyl) acrylamide, 1-(N, the N-dimethylamino)-1,1-dimethyl methyl (methyl) acrylamide and 6-(N, N-diethylamino) hexyl (methyl) acrylamide (more than be designated as aminoalkyl group (methyl) acrylic amide); To vinyl benzyl-N, N dimethylamine, to vinyl benzyl-N, N dimethylamine,, N-dihexylamine (more than be designated as the vinyl benzyl amine) to vinyl benzyl-N; And 2-vinyl pyridine, 4-vinylpridine, N-vinyl imidazole.Wherein, be preferably N, N-dimethyl aminoethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylate, 3-(N, the N-diethylamino) propyl group (methyl) acrylamide, 3-(N, N-dimethylamino) propyl group (methyl) acrylamide, 2-vinyl pyridine, 4-vinylpridine, N-vinyl imidazole.

Employed polymkeric substance can also be and the multipolymer that can form with other monomer of their copolymerization among the present invention.As can with other monomer of their copolymerization, for example can list unsaturated carboxylic acid ((methyl) vinylformic acid for example, Ba Dousuan, methylene-succinic acid, toxilic acid, and fumaric acid), aromatic ethenyl compound (for example, vinylbenzene, alpha-methyl styrene, Vinyl toluene, the 2-vinyl pyridine, 4-vinylpridine, N-vinyl imidazole etc.), (methyl) alkyl acrylate ((methyl) methyl acrylate for example, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate etc.), (methyl) acrylic acid alkyl aryl ester (for example, (methyl) vinylformic acid benzyl ester etc.), (methyl) vinylformic acid substituted alkyl ester (for example, (methyl) glycidyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate etc.), vinyl esters of carboxylic acids (for example, jealous woman vinyl acetate and propionate), vinyl cyanide (for example, (methyl) vinyl cyanide and α-Lv Bingxijing), and the aliphatics conjugated diolefine (for example, 1,3-butadiene and isoprene).Wherein, preferred unsaturated carboxylic acid, (methyl) alkyl acrylate, (methyl) acrylic acid alkyl aryl ester, vinyl esters of carboxylic acids and aromatic ethenyl compound.

The polymkeric substance that uses among the present invention be preferably by from above-mentioned formula (1-1) or (1-2) polymerizable compound of expression copolymerization units and by above-mentioned polyreactive oligomers (macromonomer) give with the multipolymer formed of repeating unit or by the repeating unit of above-mentioned formula (1-1) expression, by above-mentioned polyreactive oligomers (macromonomer) give with repeating unit and by the monomer with nitrogen-atoms to the multipolymer formed of repeating unit.The repeating unit of this multipolymer preferred formula (1-1) expression accounts for the scope that always repeats unitary 5～70 weight % (particularly 5～30 weight %).In addition, by above-mentioned polyreactive oligomers (macromonomer) give with repeating unit account for the scope that always repeats unitary 30～95 weight % (particularly 50～90 weight %), come from monomeric repeating unit and account for the scope that always repeats unitary 5～80 weight % (particularly 5～50 weight %) with nitrogenous base.

In addition, when use can be with other monomers of these repeating unit copolymerization, preferably account for the scope that always repeats unitary 5～30 weight % from this other monomeric repeating unit.The weight-average molecular weight of above-mentioned multipolymer (Mw) is preferably 1,000～200,000 scope, more preferably 10,000～100,000 scope.This weight-average molecular weight is by gel permeation chromatography (carrier: the polystyrene conversion weight-average molecular weight of Ce Lianging tetrahydrofuran (THF)).

In addition, about the structure of above-mentioned multipolymer, for example, can resolve by carrying out 1H-NMR measurement (using the measurement of Varian corporate system Mercury (300MHz)).

The example of above-mentioned graftomer that is applicable to polymkeric substance of the present invention is as follows, but the present invention is not limited to these.

1-1) monomer/terminal methyl group acryl the polymethyl methacrylate copolymer represented by M1-1 in the above-claimed cpd example

1-2) monomer/polyoxyethylene glycol one (methyl) acrylate copolymer represented by M1-1 in the above-claimed cpd example

1-3) monomer/terminal methyl group acryl polycaprolactone the multipolymer represented by M1-1 in the above-claimed cpd example

1-4) monomer/terminal methyl group acryl butyl polyacrylate the multipolymer represented by M1-1 in the above-claimed cpd example

1-5) monomer/terminal methyl group acryl the polymethyl methacrylate copolymer represented by M1-3 in the above-claimed cpd example

1-6) monomer/terminal methyl group acryl the polymethyl methacrylate copolymer represented by M1-4 in the above-claimed cpd example

1-7) monomer/polyoxyethylene glycol one (methyl) acrylate copolymer represented by M1-5 in the above-claimed cpd example

1-8) monomer/3-(N, the N-dimethylamino) propyl group acrylamide/terminal methyl group acryl polymethyl methacrylate copolymer represented by M1-1 in the above-claimed cpd example

1-9) the monomer of representing by M1-1 in the above-claimed cpd example/to vinyl benzyl-N, N dimethylamine/terminal methyl group acryl polymethyl methacrylate copolymer

1-10) monomer/3-(N, the N-dimethylamino) propyl group acrylamide/terminal methyl group acryl butyl polyacrylate multipolymer represented by M1-1 in the above-claimed cpd example

1-11) monomer/3-(N, N-dimethylamino) ethyl (methyl) acrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M1-1 in the above-claimed cpd example

1-12) monomer/2-(N, N-dimethylamino) ethyl (methyl) acrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M1-1 in the above-claimed cpd example

1-13) monomer/3-(N, N-dimethylamino) propyl group acrylamide/terminal methyl group acryl polymethylmethacrylate/polyoxyethylene glycol one (methyl) acrylate copolymer represented by M1-1 in the above-claimed cpd example

1-14) monomer/N,N-DMAA/terminal methyl group acryl the polymethyl methacrylate copolymer represented by M1-1 in the above-claimed cpd example

1-15) monomer/(methyl) methyl acrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M1-1 in the above-claimed cpd example

1-16) monomer/methacrylic acid/terminal methyl group acryl the polymethyl methacrylate copolymer represented by M1-1 in the above-claimed cpd example

1-17) monomer/(methyl) cyclohexyl acrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M1-1 in the above-claimed cpd example

1-18) monomer/(methyl) vinylformic acid 2-hydroxy methacrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M1-1 in the above-claimed cpd example

1-19) monomer/3-(N, the N-dimethylamino) propyl group acrylamide/terminal methyl group acryl polymethyl methacrylate copolymer represented by M1-7 in the above-claimed cpd example

1-20) monomer/3-(N, the N-dimethylamino) propyl group acrylamide/terminal methyl group acryl polymethyl methacrylate copolymer represented by M1-12 in the above-claimed cpd example

1-21) monomer/3-(N, N-dimethylamino) ethyl (methyl) acrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M1-13 in the above-claimed cpd example

Such graft copolymer can by make polyreactive oligomers, as required and the monomer with nitrogen-atoms and other monomer of usefulness in solvent, carry out the incompatible acquisition of radical polymerization.At this moment, preferred use radical polymerization initiator (for example, as 2,2 '-azo two (isopropyl cyanide)) (AIBN), 2,2 '-azo two-(2,4 '-methyl pentane nitrile) and so on azo-compound, the superoxide of benzoyl peroxide and so on, and the persulphate of Potassium Persulphate, ammonium persulphate and so on), but except initiator, can also add chain-transfer agent (for example, 2 mercapto ethanol and dodecyl mercaptans) comes synthetic.

＜from the monomeric macromolecular compound of formula (2-1) expression 〉

As the macromolecular compound of (B) composition that uses among the present invention can be the monomeric homopolymer of formula (2-1) expression, preferably can with other monomeric multipolymer of this monomer copolymerization, be more preferably the graft copolymer that describes in detail later.

Among the present invention, the monomeric macromolecular compound that comes from formula (2-1) expression uses as pigment dispersing agent or plays a part pigment dispersing agent, affinity height with above-mentioned (A) composition, adsorptivity to this (A) composition is good, in addition, owing to be macromolecular compound,, contain the dispersion stabilization excellence of the ink composite of the present invention of the monomeric macromolecular compound that comes from formula (2-1) expression according to the steric repulsion effect of macromolecular chain with specific repeated structural unit.Even when using in being difficult to stable dispersion De dioxazine type compound pigment dyestuff in the past, the monomeric macromolecular compound that comes from formula (2-1) expression also can demonstrate good dispersiveness.

(monomer that uses among the present invention)

The monomer that uses among the present invention is represented with following formula (2-1).

In the above-mentioned formula (2-1), R ¹Expression hydrogen atom, the alkyl of replacement and any one in the unsubstituted alkyl, R ²The expression alkylidene group, W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-and phenylene in any one, X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OC (=O) NH-,-CO-,-SO ₂-,-CH (OH) CH ₂NH-,-CH (OH) CH ₂S-,-SO ₂NH-and-any one of NHCO-, Y represents-NR ⁵-,-O-and-any one of S-, R ⁵Any one of expression hydrogen atom, alkyl and aryl, R ³, R ⁴Expression monovalence substituting group, R ³And R ⁴Can interconnection formation ring texture, m, n are respectively 0 or 1 independently.

R in the＜formula (2-1) ¹

In the above-mentioned formula (2-1), R ¹Expression hydrogen atom or replacement or unsubstituted alkyl.The carbonatoms of alkyl is preferably 1～12, and more preferably 1～8, more preferably 1～4.As alkyl, can list for example methyl, ethyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl etc.

R in the＜formula (2-1) ²

R ²The expression alkylidene group, carbonatoms is preferably 1～12, and more preferably 1～8, more preferably 1～4.As alkylidene group, can list for example methylene radical, ethylidene, propylidene, trimethylene, tetramethylene.

W in the＜formula (2-1) 〉

W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.

X in the＜formula (2-1) 〉

X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OC (=O) NH-,-CO-,-SO ₂-,-CH (OH) CH ₂NH-,-CH (OH) CH ₂S-,-SO ₂NH-or-NHCO-.

Y in the＜formula (2-1) 〉

Y represents-NR ⁵-,-O-or-S-, R ⁵Expression hydrogen atom, alkyl or aryl.The carbonatoms of alkyl is preferably 1～12, and more preferably 1～8, more preferably 1～4.As alkyl, can list for example methyl, ethyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, cyclohexyl, 2-ethylhexyl, octyl group, benzyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl etc.The carbonatoms of aryl is preferably 6～20, and more preferably 6～15.As aryl; be preferably phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 4-chloro-phenyl-, 2-p-methoxy-phenyl, 3-ethoxyl phenenyl, 4-butoxy phenyl, 2; 4-diethoxy phenyl, 4-Phenoxyphenyl, naphthyl, 4-dibutylamino formyl radical phenyl, 4-dibutylamine alkylsulfonyl phenyl, more preferably phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 4-chloro-phenyl-, 2-p-methoxy-phenyl, 3-ethoxyl phenenyl, 4-butoxy phenyl.

M, n in the＜formula (2-1) 〉

M, n are respectively 0 or 1 independently.

R in the＜formula (2-1) ³, R ⁴

R ³, R ⁴Expression monovalence substituting group.R ³And R ⁴Can interconnection formation ring texture.R in the formula (2-1) ³, R ⁴The substituent object lesson of monovalence of expression and the R in the formula (1-1) ³, R ⁴The substituent object lesson of monovalence of expression is identical, and preferred range is also identical.

In addition, the monomer that uses among the present invention is preferably used following formula (2-2) expression.

In the formula (2-2), R ¹Expression hydrogen atom or replacement or unsubstituted alkyl.R ³, R ⁴Expression monovalence substituting group.R ³And R ⁴Can interconnection formation ring texture.The example of preferred substituted is identical with the situation of above-mentioned formula (2-1).

Y, Z difference is expression-NR independently ⁵-,-O-or-S-, R ⁵Expression hydrogen atom, alkyl or aryl.The example of preferred substituted is identical with the situation of above-mentioned formula (2-1).

In addition, the monomer that uses among the present invention is preferably used following formula (2-3) expression.

In the formula (2-3), R ¹Expression hydrogen atom or replacement or unsubstituted alkyl.R ³, R ⁴Expression monovalence substituting group.R ³And R ⁴Can interconnection formation ring texture.The example of preferred substituted is identical with the situation of above-mentioned formula (2-1).

Y represents-NR ⁵-,-O-or-S-, R ⁵Expression hydrogen atom, alkyl or aryl.The example of preferred substituted is identical with the situation of above-mentioned formula (2-1).

Preferred object lesson as the compound of formula (2-1), formula (2-2) or formula (2-3) expression is listed below.In addition, the present invention is not limited to this.

(macromolecular compound)

The macromolecular compound that uses among the present invention is the polymkeric substance that contains the copolymerization units of the polymerizable compound of representing from above-mentioned formula (2-1)～formula (2-3) (monomer).

Above-mentioned macromolecular compound preferably also contains the polyreactive oligomers that the has the ethylenic unsaturated double-bond endways graft copolymer as copolymerization units.This have the polyreactive oligomers of ethylenic unsaturated double-bond endways owing to be the compound with regulation molecular weight, so be also referred to as macromonomer.

As polyreactive oligomers, can list the polyreactive oligomers of above-mentioned formula (1-3) expression and the polyreactive oligomers of above-mentioned formula (1-4) expression, preferred range is also identical.

In addition, the polymkeric substance of the present invention's use can also be the multipolymer that forms with the monomer with nitrogen-atoms.As monomer, can list the above-mentioned monomer with nitrogen-atoms of for example conduct from the copolymer composition of the monomeric macromolecular compound of formula (1-1) expression with nitrogen-atoms.

The multipolymer that the present invention uses can also be and the multipolymer that can form with other monomer of their copolymerization.As with they can copolymerization other monomer, for example can list as above-mentioned other monomer from the copolymer composition of the monomeric macromolecular compound of formula (1-1) expression.

The polymkeric substance that uses among the present invention be preferably by from the copolymerization units of the polymerizable compound of above-mentioned formula (2-1)～formula (2-3) expression and by above-mentioned polyreactive oligomers (macromonomer) give with the multipolymer formed of repeating unit or by the repeating unit of above-mentioned formula (2-1) expression, by above-mentioned polyreactive oligomers (macromonomer) give with repeating unit and by the monomer with nitrogen-atoms to the multipolymer formed of repeating unit.The repeating unit of this multipolymer preferred formula (2-1)～formula (2-3) expression accounts for the scope that always repeats unitary 5～70 weight % (particularly 5～30 weight %).In addition, by above-mentioned polyreactive oligomers (macromonomer) give with repeating unit account for the scope that always repeats unitary 30～95 weight % (particularly 50～90 weight %), account for the scope that always repeats unitary 5～80 weight % (particularly 5～50 weight %) from monomeric repeating unit with nitrogenous base.

In addition, when use can be with other monomers of these repeating unit copolymerization, preferably account for the scope that always repeats unitary 5～30 weight % from this other monomeric repeating unit.The weight-average molecular weight of above-mentioned multipolymer (Mw) is preferably 1,000～200,000 scope, more preferably 10,000～100,000 scope.This weight-average molecular weight is by gel permeation chromatography (carrier: the polystyrene conversion weight-average molecular weight of Ce Lianging tetrahydrofuran (THF)).

In addition, about the structure of above-mentioned multipolymer, for example, can be by carrying out ¹H-NMR measures (using the measurement of Varian corporate system Mercury (300MHz)) and resolves.

The example of above-mentioned graftomer that is applicable to polymkeric substance used among the present invention is as follows, but the present invention is not limited to these.

2-1) monomer/terminal methyl group acryl the polymethyl methacrylate copolymer represented by M2-1 in the above-claimed cpd example

2-2) monomer/polyoxyethylene glycol one (methyl) acrylate copolymer represented by M2-1 in the above-claimed cpd example

2-3) monomer/terminal methyl group acryl polycaprolactone the multipolymer represented by M2-1 in the above-claimed cpd example

2-4) monomer/terminal methyl group acryl butyl polyacrylate the multipolymer represented by M2-1 in the above-claimed cpd example

2-5) monomer/terminal methyl group acryl the polymethyl methacrylate copolymer represented by M2-2 in the above-claimed cpd example

2-6) monomer/terminal methyl group acryl the polymethyl methacrylate copolymer represented by M2-2 in the above-claimed cpd example

2-7) monomer/polyoxyethylene glycol one (methyl) acrylate copolymer represented by M2-5 in the above-claimed cpd example

2-8) monomer/3-(N, the N-dimethylamino) propyl group acrylamide/terminal methyl group acryl polymethyl methacrylate copolymer represented by M2-1 in the above-claimed cpd example

2-9) the monomer of representing by M2-1 in the above-claimed cpd example/to vinyl benzyl-N, N dimethylamine/terminal methyl group acryl polymethyl methacrylate copolymer

2-10) monomer/3-(N, the N-dimethylamino) propyl group acrylamide/terminal methyl group acryl butyl polyacrylate multipolymer represented by M2-1 in the above-claimed cpd example

2-11) monomer/3-(N, N-dimethylamino) (methyl) ethyl (methyl) acrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M2-1 in the above-claimed cpd example

2-12) monomer/2-(N, N-dimethylamino) ethyl (methyl) acrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M2-13 in the above-claimed cpd example

2-13) monomer/3-(N, N-dimethylamino) propyl group acrylamide/terminal methyl group acryl polymethylmethacrylate/polyoxyethylene glycol one (methyl) acrylate copolymer represented by M2-1 in the above-claimed cpd example

2-14) monomer/N,N-DMAA/terminal methyl group acryl the polymethyl methacrylate copolymer represented by M2-15 in the above-claimed cpd example

2-15) monomer/(methyl) methyl acrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M2-1 in the above-claimed cpd example

2-16) monomer/methacrylic acid/terminal methyl group acryl the polymethyl methacrylate copolymer represented by M2-1 in the above-claimed cpd example

2-17) monomer/(methyl) cyclohexyl acrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M2-1 in the above-claimed cpd example

2-18) monomer/(methyl) vinylformic acid 2-hydroxy methacrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M2-1 in the above-claimed cpd example

2-19) monomer/3-(N, the N-dimethylamino) propyl group acrylamide/terminal methyl group acryl polymethyl methacrylate copolymer represented by M2-7 in the above-claimed cpd example

2-20) monomer/3-(N, the N-dimethylamino) propyl group acrylamide/terminal methyl group acryl polymethyl methacrylate copolymer represented by M2-10 in the above-claimed cpd example

2-21) monomer/3-(N, N-dimethylamino) (methyl) ethyl (methyl) acrylate/terminal methyl group acryl polymethyl methacrylate copolymer represented by M2-19 in the above-claimed cpd example

Such graft copolymer can by make polyreactive oligomers, as required and the monomer with nitrogen-atoms and other monomer of usefulness in solvent, carry out the incompatible acquisition of radical polymerization.At this moment, usually (for example use radical polymerization initiator, as 2,2 '-azo two (isopropyl cyanide)) (AIBN), 2,2 '-azo two-(2,4 '-methyl pentane nitrile) azo-compound, as the superoxide of benzoyl peroxide, and as the persulphate of Potassium Persulphate, ammonium persulphate), but except initiator, can also add chain-transfer agent (for example, 2 mercapto ethanol and dodecyl mercaptans) comes synthetic.

＜(B) polymkeric substance of formula (3-1) expression 〉

The polymkeric substance of following formula (3-1) expression is owing to the end at polymkeric substance has a plurality of 1 valency organic groups as follows, promptly this 1 valency organic group contains by being selected from the organic pigment structure, heterocycle structure, acidic groups, group with basic nitrogen atom, urea groups, carbamate groups, group with coordination Sauerstoffatom, carbonatoms is the alkyl more than 4, carbonatoms is the alkoxysilyl below 6, epoxy group(ing), isocyanate group, and the pigment adsorption structure of at least a kind of formation in the hydroxyl, so have outstanding adsorptivity to solid surface, outstanding micelle formation ability, various features such as surfactivity or function are suitable as pigment dispersing agent.

＜1 valency organic group: A ¹

In the above-mentioned formula (3-1), A ¹It is that alkyl, carbonatoms more than 4 is 1 valency organic group of at least a pigment adsorption structure that constitutes in alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl below 6 that expression contains by being selected from organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, carbonatoms, n A ¹Can be identical or different.

At an A ¹In, as long as contain at least a above-mentioned pigment adsorption structure, also can contain two or more.

Above-mentioned 1 valency organic group is organic linking group be combined into of constituting by above-mentioned pigment adsorption structure with by 1～200 carbon atom, the nitrogen-atoms below 20, the Sauerstoffatom below 100,1～400 hydrogen atom and the sulphur atom below 40.

Also have, above-mentioned pigment adsorption structure itself also can constitute above-mentioned 1 valency organic group.

-pigment adsorption structure-

Below to constituting above-mentioned A ¹Above-mentioned pigment adsorption structure describe.

As the above-mentioned organic pigment structure of one of above-mentioned pigment adsorption structure, can preferably list for example phthalocyanines, insoluble azo class, azo lake class, anthraquinone class, quinacridine ketone, dioxazines, diketopyrrolo-pyrrole (diketopyrrolopyrrole) class, anthra pyridines, anthanthrone (ア Application サ Application ス ロ Application) class, indanthrone class, flavanthrones, purple cyclic ketones (perinone) class, perylene class, thioindigo class pigment structure etc.Wherein, preferred phthalocyanines, azo lake class, anthraquinone class, dioxazines, diketopyrrolo-pyrrole class pigment structure, more preferably phthalocyanines, anthraquinone class, diketopyrrolo-pyrrole class pigment structure.

As the above-mentioned heterocycle structure of one of above-mentioned pigment adsorption structure, for example can preferably enumerate thiophene, furans, xanthene, the pyrroles, pyrroline, tetramethyleneimine, dioxolane, pyrazoles, pyrazoline, pyrazolidine, imidazoles oxazole, thiazole oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithian, isoindoline, isoindoline ketone, benzimidazolone, benzothiazole, succinimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, carbazole, acridine, dihydroketoacridine, anthraquinone etc.Wherein, preferred pyrroline, tetramethyleneimine, pyrazoles, pyrazoline, pyrazolidine, imidazoles, triazole, pyridine, piperidines, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindoline ketone, benzimidazolone, benzothiazole, succinimide, phthalic imidine, naphthalimide, glycolylurea, carbazole, acridine, dihydroketoacridine, anthraquinone.

In addition, above-mentioned organic pigment structure or above-mentioned heterocycle structure also can further have substituting group, as this substituting group, for example can list carbonatoms and be 1～20 alkyl (methyl, ethyl etc.), carbonatoms is 6～16 aryl (phenyl, naphthyl etc.), hydroxyl, amino, carboxyl, sulfoamido, N-sulphonyl amide group, carbonatoms are 1～6 acyloxy (acetoxyl group etc.), and carbonatoms is 1～20 alkoxyl group (methoxyl group, oxyethyl group etc.), halogen atom (chlorine, bromine etc.), carbonatoms is 2～7 carbalkoxy (methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyls etc.), cyano group, carbonatoms are carbonate group (tertiary butyl carbonic ether etc.) of 2～10 etc.At this, these substituting groups also can combine with above-mentioned organic pigment structure or above-mentioned heterocycle structure by following structural unit or its linking group group that constitutes.

As the above-mentioned acidic groups of one of above-mentioned pigment adsorption structure, can preferably enumerate for example carboxylic acid group, sulfonic group, a sulfate group, phosphonate group, a phosphonate group, boronate.Wherein, optimization acid's base, sulfonic group, a sulfate group, phosphonate group, a phosphonate group, more preferably carboxylic acid group, sulfonic group, phosphonate group.

As the above-mentioned group of one of above-mentioned pigment adsorption structure, for example can preferably enumerate amino (NH with basic nitrogen atom ₂), substituted-amino (NHR ⁸,-MR ⁹R ¹⁰, at this, R ⁸, R ⁹And R ¹⁰Represent that independently of one another carbonatoms is that 1～20 alkyl, carbonatoms are that 6～20 aryl, carbonatoms are 7～20 aralkyl), by the guanidine radicals of following formula (a1) expression, by the amidino groups (amidinyl) of following formula (a2) expression etc.

In the above-mentioned formula (a1), R ¹¹And R ¹²Represent that independently of one another carbonatoms is that 1～20 alkyl, carbonatoms are that 6～20 aryl, carbonatoms are 7～20 aralkyl.

In the above-mentioned formula (a2), R ¹³And R ¹⁴Represent that independently of one another carbonatoms is that 1～20 alkyl, carbonatoms are that 6～20 aryl, carbonatoms are 7～20 aralkyl.

Wherein, preferred amino (NH ₂), substituted-amino (NHR ⁸,-NR ⁹R ¹⁰, at this, R ⁸, R ⁹And R ¹⁰Represent that independently of one another carbonatoms is 1～10 alkyl, phenyl or benzyl.), by the guanidine radicals of above-mentioned formula (a1) expression [in the formula (a1), R ¹¹And R ¹²Represent that independently of one another carbonatoms is 1～10 alkyl, phenyl or benzyl.], by the amidino groups of above-mentioned formula (a2) expression [in the formula (a2), R ¹³And R ¹⁴Represent that independently of one another carbonatoms is 1～10 alkyl, phenyl or benzyl.] etc., preferred especially amino (NH ₂), substituted-amino (NHR ⁸,-NR ⁹R ¹⁰, at this, R ⁸, R ⁹And R ¹⁰Represent that independently of one another carbonatoms is 1～5 alkyl, phenyl or benzyl.), by the guanidine radicals of above-mentioned formula (a1) expression [in the formula (a1), R ¹¹And R ¹²Represent that independently of one another carbonatoms is 1～5 alkyl, phenyl or benzyl.], by the amidino groups of above-mentioned formula (a2) expression [in the formula (a2), R ¹³And R ¹⁴Represent that independently of one another carbonatoms is 1～5 alkyl, phenyl or benzyl.] etc.

As the above-mentioned urea groups of one of above-mentioned pigment adsorption structure, for example can preferably enumerate-NR ¹⁵CONR ¹⁶R ¹⁷(at this, R ¹⁵, R ¹⁶And R ¹⁷Represent that independently of one another hydrogen atom or carbonatoms are that 1～20 alkyl, carbonatoms are that aryl more than 6 or carbonatoms are the aralkyl more than 7.)。Wherein, preferred-NR ¹⁵CONR ¹⁷(at this, R ¹⁵And R ¹⁷Represent that independently of one another hydrogen atom or carbonatoms are that 1～10 alkyl, carbonatoms are that 6～20 aryl or carbonatoms are 7～20 aralkyl), more preferably-NHCONHR ¹⁷(at this, R ¹⁷Expression hydrogen atom or carbonatoms are that 1～10 alkyl, carbonatoms are that 6～15 aryl or carbonatoms are 7～15 aralkyl).

As the above-mentioned carbamate groups of one of above-mentioned pigment adsorption structure, for example can preferably enumerate-NHCOOR ¹⁸,-NR ¹⁹COOR ²⁰,-OCONHR ²¹,-OCONR ²²R ²³(at this, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²²And R ²³Represent that independently of one another carbonatoms is that 1～20 alkyl, carbonatoms are that 6～20 aryl or carbonatoms are 7～20 aralkyl) etc.Wherein, preferred-NHCOOR ¹⁸,-OCONHR ²¹(at this, R ¹⁸, R ²¹Represent that independently of one another carbonatoms is that 1～20 alkyl, carbonatoms are that 6～20 aryl or carbonatoms are 7～20 aralkyl) etc., more preferably-NHCOOR ¹⁸,-OCONHR ²¹(at this, R ¹⁸, R ²¹Represent that independently of one another carbonatoms is that 1～10 alkyl, carbonatoms are that 6～15 aryl or carbonatoms are 7～15 aralkyl) etc.

Above-mentioned group with coordination Sauerstoffatom as one of above-mentioned pigment adsorption structure for example can list methyl ethyl diketone perester radical, crown ether base etc.

As the above-mentioned carbonatoms of one of above-mentioned pigment adsorption structure is alkyl more than 4, and aryl, the carbonatoms that can preferably enumerate carbonatoms and be alkyl, carbonatoms more than 4 and be more than 6 are aralkyl more than 7 etc.Wherein, preferred carbonatoms is that 4～20 alkyl, carbonatoms are that 6～20 aryl, carbonatoms are 7～20 aralkyl etc., and more preferably carbonatoms is that 4～15 alkyl (for example octyl group, dodecyl etc.), carbonatoms are that 6～15 aryl (for example phenyl, naphthyl etc.), carbonatoms are 7～15 aralkyl (for example benzyl etc.) etc.

As the above-mentioned alkoxysilyl of one of above-mentioned pigment adsorption structure, for example can list carbonatoms and be the alkoxysilyl below 6, can list for example trimethoxysilyl, triethoxysilyl etc.

-organic linking group-

As above-mentioned organic linking group, preferred singly-bound or the organic linking group that is made of 1～100 carbon atom, the nitrogen-atoms below 10, the Sauerstoffatom below 50,1～200 hydrogen atom and the sulphur atom below 20, this organic linking group can be substituted base and replace.

As the object lesson of above-mentioned organic linking group, can preferably enumerate following structural unit or its group that constitutes etc.

Have under the substituent situation at above-mentioned organic linking group, as this substituting group, for example can list carbonatoms and be 1～20 alkyl (methyl, ethyl etc.), carbonatoms is 6～16 aryl (phenyl, naphthyl etc.), hydroxyl, amino, carboxyl, sulfoamido, N-sulphonyl amide group, carbonatoms is 1～6 acyloxy (acetoxyl group etc.), carbonatoms is 1～6 alkoxyl group (methoxyl group, oxyethyl group etc.), chlorine, halogen atoms such as bromine, carbonatoms are 2～7 carbalkoxy (methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl etc.), cyano group, carbonatoms are 2～10 carbonate group (tertiary butyl carbonic ether etc.) etc.

Among the present invention, as above-mentioned A ¹Be preferably and contain by being selected from above-mentioned organic pigment structure, above-mentioned heterocycle structure, above-mentioned acidic groups, above-mentionedly having the 1 valency organic group that the group of basic nitrogen atom, above-mentioned urea groups and above-mentioned carbonatoms are at least a pigment adsorption structure that constitutes in the alkyl more than 4,1 a valency organic group of more preferably following formula (3-4) expression.

In above-mentioned formula (3-4), B ¹Represent above-mentioned pigment adsorption structure (promptly, by being that alkyl, carbonatoms more than 4 is at least a structure of selecting alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl below 6 of forming from organic pigment structure, heterocycle structure, acidic groups, group, urea groups, carbamate groups, group, carbonatoms with coordination Sauerstoffatom with basic nitrogen atom), R ²⁴Expression singly-bound or (a+1) organic linking group of valency.A represents 1～10 integer, is preferably 1～7, more preferably 1～5, be preferably 1～3 especially.A B ¹Identical group can be, also different groups can be.In addition, as organic linking group of above-mentioned (a+1) valency, can list the group that constitutes by 1～100 carbon atom, the nitrogen-atoms below 10, the Sauerstoffatom below 50,1～200 hydrogen atom and the sulphur atom below 20.In organic linking group that should (a+1) valency, the especially preferred organic linking group that constitutes by 1～10 carbon atom, the nitrogen-atoms below 5, the Sauerstoffatom below 10,1～30 hydrogen atom and the sulphur atom below 5.

As by above-mentioned B ¹The above-mentioned pigment adsorption structure of expression can list and the A that constitutes in the above-mentioned formula (3-1) ¹The identical adsorption structure of pigment adsorption structure, preference is also identical.Wherein, preferably by from organic pigment structure, heterocycle structure, acidic groups, group, urea groups and carbonatoms being at least a pigment adsorption structure of selecting the alkyl more than 4 that constitutes with basic nitrogen atom.

Object lesson as organic linking group of above-mentioned (a+1) valency can list following structural unit or its group that constitutes (can form ring structure) etc.

-

Organic linking group of above-mentioned (a+1) valency can be substituted base and replace, as this substituting group, for example can list carbonatoms and be 1～20 alkyl (methyl, ethyl etc.), carbonatoms is 6～16 aryl (phenyl, naphthyl etc.), hydroxyl, amino, carboxyl (acetoxyl group etc.), sulfoamido, N-sulphonyl amide group, carbonatoms is 1～6 acyloxy, carbonatoms is 1～6 alkoxyl group (methoxyl group, oxyethyl group etc.), halogen atom (chlorine, bromines etc.), carbonatoms is 2～7 carbalkoxy (methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl etc.), cyano group, carbonatoms are 2～10 carbonate group (tertiary butyl carbonic ether etc.) etc.

<R ²>

In above-mentioned formula (3-1), R ²Expression singly-bound or the organic linking group of divalent.N R ²Can be identical, also can be different.

As the organic linking group of divalent, can preferably list the group that constitutes by 1～100 carbon atom, the nitrogen-atoms below 10, the Sauerstoffatom below 50,1～200 hydrogen atom and the sulphur atom below 20, also can be substituted base and replace.

As the object lesson of the organic linking group of above-mentioned divalent, can list following structural unit or its group that constitutes.

As above-mentioned R ²Be preferably singly-bound or by 1～50 carbon atom, nitrogen-atoms below 8, Sauerstoffatom below 25, the organic linking group of divalent that 1～100 hydrogen atom and the sulphur atom below 10 constitute, singly-bound or more preferably by 1～30 carbon atom, nitrogen-atoms below 6, Sauerstoffatom below 15, the organic linking group of divalent that 1～50 hydrogen atom and the sulphur atom below 7 constitute is preferably singly-bound or especially by 1～10 carbon atom, nitrogen-atoms below 5, Sauerstoffatom below 10, the organic linking group of divalent that 1～30 hydrogen atom and the sulphur atom below 5 constitute.

Have under the substituent situation at the organic linking group of above-mentioned divalent, as this substituting group, for example can list carbonatoms and be 1～20 alkyl (methyl, ethyl etc.), carbonatoms is 6～16 aryl (phenyl, naphthyl etc.), hydroxyl, amino, carboxyl (acetoxyl group etc.), sulfoamido, N-sulphonyl amide group, carbonatoms is 1～6 acyloxy, carbonatoms is 1～6 alkoxyl group (methoxyl group, oxyethyl group etc.), halogen atom (chlorine, bromines etc.), carbonatoms is 2～7 carbalkoxy (methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl etc.), cyano group, carbonate group (tertiary butyl carbonic ether etc.) etc.

<R ¹>

In above-mentioned formula (3-1), R ¹Organic linking group of expression (m+n) valency.M+n is 3～10.

As above-mentioned R ¹Organic linking group of (m+n) valency of expression comprises the group that is made of 1～100 carbon atom, the nitrogen-atoms below 10, the Sauerstoffatom below 50,1～200 hydrogen atom and the sulphur atom below 20, also can be substituted base and replace.

As the object lesson of organic linking group of above-mentioned (m+n), can preferably enumerate following structural unit or its group that constitutes (can form ring structure) etc.

Organic linking group as (m+n) valency, be preferably the group that constitutes by 1～60 carbon atom, the nitrogen-atoms below 10, the Sauerstoffatom below 40,1～120 hydrogen atom and the sulphur atom below 10, the group that is made of 1～50 carbon atom, the nitrogen-atoms below 10, the Sauerstoffatom below 30,1～100 hydrogen atom and the sulphur atom below 7 more preferably is preferably the group that is made of 1～40 carbon atom, the nitrogen-atoms below 8, the Sauerstoffatom below 20,1～80 hydrogen atom and the sulphur atom below 5 especially.

Organic linking group at above-mentioned (m+n) valency has under the substituent situation, as this substituting group, for example can list carbonatoms and be 1～20 alkyl (methyl, ethyl etc.), carbonatoms is 6～16 aryl (phenyl, naphthyl etc.), hydroxyl, amino, carboxyl (acetoxyl group etc.), sulfoamido, N-sulphonyl amide group, carbonatoms is 1～6 acyloxy, carbonatoms is 1～6 alkoxyl group (methoxyl group, oxyethyl group etc.), halogen atom (chlorine, bromines etc.), carbonatoms is 2～7 carbalkoxy (methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl etc.), cyano group, carbonatoms are 2～10 carbonate group (tertiary butyl carbonic ether etc.) etc.

Here, by above-mentioned R ¹The object lesson [(1)～(17)] of organic linking group of above-mentioned (m+n) valency of expression is as follows.But, scope of the present invention is not limited to these.

＜m and n 〉

In above-mentioned formula (3-1), m represents 1～8, is preferably 1～5, more preferably 1～4, be preferably 1～3 especially.

In addition, n represents 2～9, is preferably 2～8, more preferably 2～7, be preferably 3～6 especially.

<P ¹>

In above-mentioned formula (3-1), P ¹The expression polymer backbone can be from known polymkeric substance etc. waits according to purpose and selects.M P ¹Can be identical, also can be different.

In the above-mentioned polymkeric substance, as the polymkeric substance that constitutes polymer backbone, preferably [multipolymer etc. that for example comprises polyethers/polyurethane copolymer, polyethers/polymer of vinyl monomer (can be any one of random copolymers, segmented copolymer, graft copolymer from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, polyurethane polymer, acylamide polymer, epoxide polymer, type siloxane polymkeric substance and their modifier or multipolymer.)。] select in the group that constitutes at least a, that more preferably selects from the group of polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, polyurethane polymer and their modifier or multipolymer formation is at least a, special preferred vinyl polymer of monomers or multipolymer.

And then above-mentioned polymkeric substance preferably dissolves in organic solvent.When the affinity of above-mentioned polymkeric substance and above-mentioned organic solvent is hanged down, for example when the pigment dispersing agent, sometimes with the affinity of dispersion medium a little less than, can not guarantee adsorption layer enough for decentralized stabilization.

As above-mentioned vinyl monomer, for example can list (methyl) esters of acrylic acid, crotonate class, vinyl ester, maleic acid diester class, dimethyl ester class, methylene-succinic acid diester class, (methyl) acrylic amide, styrenic, ethene ethers, vinyl ketones, olefines, maleimide, (methyl) vinyl cyanide, have the vinyl monomer of acidic groups etc.

As above-mentioned (methyl) esters of acrylic acid, can list for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid uncle monooctyl ester, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid 3-hydroxy-propyl ester, (methyl) vinylformic acid 4-hydroxybutyl ester, (methyl) vinylformic acid 2-methoxy ethyl ester, (methyl) vinylformic acid 2-ethoxyethyl group ester, (methyl) vinylformic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) vinylformic acid 3-phenoxy group-2-hydroxy-propyl ester, (methyl) vinylformic acid 2-chloro-ethyl ester, (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-oxyethyl group cyclohexyl methyl ester, (methyl) vinylformic acid vinyl ester, (methyl) vinylformic acid 2-phenyl vinyl ester, (methyl) vinylformic acid 1-propenyl ester, (methyl) vinylformic acid allyl ester, (methyl) vinylformic acid 2-allyloxy ethyl ester, (methyl) vinylformic acid propargyl ester, (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid diethylene glycol monomethyl ether, (methyl) vinylformic acid ethyl carbitol, (methyl) vinylformic acid triglycol monomethyl ether, (methyl) vinylformic acid triglycol one ether, (methyl) polyalkylene glycol acrylate monomethyl ether, (methyl) polyalkylene glycol acrylate one ether, (methyl) vinylformic acid beta-phenoxy ethoxy ethyl ester, (methyl) vinylformic acid Nonylphenoxy polyoxyethylene glycol, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid two cyclopentenes oxygen base ethyl esters, (methyl) vinylformic acid trifluoroethyl ester, (methyl) vinylformic acid octafluoro amyl group ester, (methyl) vinylformic acid perfluoro capryl ethyl ester, (methyl) vinylformic acid two ring pentyl esters, (methyl) vinylformic acid tribromo phenylester, (methyl) vinylformic acid tribromophenoxy ethyl ester, (methyl) vinylformic acid gamma-butyrolactone etc.

As above-mentioned crotonate class, can list for example butyl crotonate and the own ester of Ba Dousuan etc.

As above-mentioned vinyl ester, can list for example vinyl-acetic ester, vinyl chloroacetate, propionate, vinyl butyrate, methoxyacetic acid vinyl acetate and vinyl benzoate etc.

As the maleic acid diester class, can list for example dimethyl maleate, ethyl maleate and dibutyl maleinate etc.

As above-mentioned dimethyl ester class, can list for example dimethyl fumarate, DEF, dibutyl fumarate etc.

As above-mentioned methylene-succinic acid diester class, can list for example dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.

As above-mentioned (methyl) acrylic amide, can list for example (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide, N-cyclohexyl (methyl) acrylamide, N-(2-methoxy ethyl) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-phenyl (methyl) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N phenyl acrylamide, N-benzyl (methyl) acrylamide, (methyl) acryloyl morpholine, diacetone acrylamide, N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, vinyl (methyl) acrylamide, N, N-diallyl (methyl) acrylamide, N-allyl group (methyl) acrylamide etc.

As above-mentioned styrenic, can list for example vinylbenzene, vinyl toluene, dimethyl styrene, Three methyl Benzene ethene, ethyl styrene, isopropyl benzene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chloro-styrene, dichlorostyrene, bromstyrol, 1-chloro-4-methyl-benzene, can be utilized hydroxy styrenes, vinyl benzoic acid methyl esters and the alpha-methyl styrene etc. of group (for example t-Boc etc.) protection of acidic substance deprotection.

As above-mentioned ethene ethers, can list for example ethylene methacrylic ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl Vinyl Ether, propyl vinyl ether, butyl vinyl ether, hexyl Vinyl Ether, octyl group Vinyl Ether, methoxy ethyl Vinyl Ether and phenylvinyl ether etc.

As above-mentioned vinyl ketones, can list for example methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone etc.

As above-mentioned olefines, can list for example ethene, propylene, iso-butylene, divinyl, isoprene etc.

As above-mentioned maleimide, can list for example maleimide, butyl maleimide, cyclohexyl maleimide, phenyl maleimide etc.

As above-mentioned vinyl monomer, except above-mentioned those, above-mentioned (methyl) vinyl cyanide, can also use heterocyclic radical (for example vinyl pyridine, N-vinyl pyrrolidone, vinylcarbazole etc.), N-vinyl formamide, N-vinyl acetamide, N-vinyl imidazole, vinyl caprolactone of vinyl substituted etc.In addition, can also use the vinyl monomer of functional groups such as for example having carbamate groups, urea groups, sulfoamido, phenylol, imide.It is synthetic aptly that the vinyl monomer with carbamate groups or urea groups so for example can utilize isocyanate group and hydroxyl or amino addition reaction.Particularly, can utilize the monomer that contains isocyanate group and contain the compound of 1 hydroxyl or contain the addition reaction of the compound of 1 uncle or secondary amino group, perhaps the addition reaction of the monomer of hydroxyl or the monomer that contains uncle or secondary amino group and an isocyanic ester waits aptly and synthesizes.

As above-mentioned vinyl monomer with acidic groups, can list the vinyl monomer that for example has carboxyl or have sulfonic vinyl monomer, have phosphonate group vinyl monomer, contain the phenol hydroxyl vinyl monomer, contain the vinyl monomer of sulfoamido etc.

As above-mentioned vinyl monomer, for example can list (methyl) vinylformic acid, vinyl benzoic acid, toxilic acid, toxilic acid one alkyl ester, fumaric acid, methylene-succinic acid, Ba Dousuan, styracin, acrylic acid dimer etc. with carboxyl.In addition, can also utilize (methyl) vinylformic acid 2-hydroxyethyl ester etc. to have the addition reaction of the cyclic acid anhydride of the monomer of hydroxyl and maleic anhydride or Tetra hydro Phthalic anhydride, cyclohexane cyclohexanedimethanodibasic acid anhydride and so on, ω-carboxyl-polycaprolactone one (methyl) acrylate etc.In addition, as the presoma of carboxyl, also can use maleic anhydride, itaconic anhydride, citraconic anhydride etc. to contain anhydride monomers.In addition, in these, consider preferred especially (methyl) vinylformic acid from viewpoints such as copolymerization, cost, solvabilities.

Have a sulfonic vinyl monomer as above-mentioned, can list for example 2-acrylamide-2-methyl propane sulfonic acid etc.

As above-mentioned vinyl monomer, can list for example phosphonic acids list (2-acryloxy ethyl ester), phosphonic acids list (1-methyl-2-acryloxy ethyl ester) etc. with phosphonate group.

Among the present invention, in polymkeric substance by above-mentioned formula (3-1) expression, the polymkeric substance of preferred following formula (3-2) expression.

In above-mentioned formula (3-2), A ²With the above-mentioned A in the above-mentioned formula (3-1) ¹Implication identical, preferred version is also identical.

R ⁴, R ⁵Represent the organic linking group of singly-bound or divalent independently of one another.N R ⁴, a m R ⁵Can be identical or different independently of one another.R ⁴, R ⁵With the above-mentioned R in the above-mentioned formula (3-1) ²Implication identical, preferred version is also identical.

In above-mentioned formula (3-2), R ³Organic linking group of expression (m+n) valency.M+n is 3～10.

As above-mentioned by R ³Organic linking group of (m+n) valency of expression for example comprises the group that is made of 1～60 carbon atom, the nitrogen-atoms below 10, the Sauerstoffatom below 50,1～100 hydrogen atom and the sulphur atom below 20, also can be substituted base and replace.

As above-mentioned by R ³Organic linking group of above-mentioned (m+n) valency of expression is with above-mentioned R ¹In the implication of organic linking group of (m+n) valency identical, its preferred version is also identical.

In above-mentioned formula (3-2), m represents 1～8, and is preferred 1～5, more preferably 1～4, preferred especially 1～3.N represents 2～9, and is preferred 2～8, more preferably 2～7, preferred especially 3～6.

In above-mentioned formula (3-2), P ²The expression macromolecular scaffold can be from known polymkeric substance etc. waits according to purpose and selects.M P ²Can be identical, also can be different.For the preferred version of above-mentioned polymkeric substance, with the P in the above-mentioned formula (3-1) ¹Implication identical, its preferred version is also identical.

In the polymkeric substance of above-mentioned formula (3-2) expression, most preferably satisfy R shown below ³, R ⁴, R ⁵, P ², m and n the polymkeric substance of all conditions.

R ³: above-mentioned object lesson (1), (2), (10), (11), (16) or (17)

R ⁴: the organic linking group of divalent that is made of " 1～10 carbon atom; the nitrogen-atoms below 5; Sauerstoffatom below 10; 1～30 hydrogen atom and 0～5 's sulphur atom " that singly-bound or following structural unit or its constitute (can have substituting group, as this substituting group, for example can list carbonatoms and be 1～20 alkyl (methyl, ethyl etc.), carbonatoms is 6～16 aryl (phenyl, naphthyl etc.), hydroxyl, amino, carboxyl (acetoxyl group etc.), sulfoamido, N-sulphonyl amide group, carbonatoms is 1～6 acyloxy, carbonatoms is 1～6 alkoxyl group (methoxyl group, oxyethyl group etc.), halogen atom (chlorine, bromine etc.), carbonatoms is 2～7 carbalkoxy (methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl etc.), cyano group, carbonatoms are 2～10 carbonate group (tertiary butyl carbonic ether etc.) etc.

R ⁵: singly-bound, ethylidene, propylidene, following radicals (a) or following radicals (b) in addition, in the following radicals, R ²⁵Expression hydrogen atom or methyl, 1 expression 1 or 2.

P ²: polymer of vinyl monomer or multipolymer, esters monomer, ethers monomer, polyurethane polymer and their modifier

m：1～3

n：3～6。

Molecular weight as the polymkeric substance of above-mentioned formula (3-1) expression is preferably 3000～100000 in weight-average molecular weight, and more preferably 5000～80000, be preferably 7000～60000 especially.

If above-mentioned weight-average molecular weight is in the above-mentioned scope, then the effect of a plurality of above-mentioned adsorption sites that import to the end of polymkeric substance is brought into play fully, has given play to the excellent adsorptivity to solid surface, micelle formation ability, surface-active performance.Especially in that the macromolecular compound among the present invention is used as under the situation of pigment dispersing agent, can realize good dispersiveness and dispersion stabilization.

The following method of for example can utilizing the polymkeric substance of above-mentioned formula (3-1) expression (comprising the polymkeric substance by formula (3-2) expression) waits to synthesize, promptly

The method of high molecular weight reactive takes place in the isocyanic ester etc. that 1) make the polymkeric substance that has imported the functional group that selects endways from carboxyl, hydroxyl, amino etc. and the acyl halide with a plurality of above-mentioned adsorption sites, has the alkylogen of a plurality of above-mentioned adsorption sites or have a plurality of above-mentioned adsorption sites;

2) make polymkeric substance that has imported carbon-to-carbon double bond endways and mercaptan that the method for Michael addition reaction take place with a plurality of above-mentioned adsorption sites;

3) method that polymkeric substance that has imported carbon-to-carbon double bond endways and the mercaptan with above-mentioned adsorption site are reacted in the presence of free radical generating agent;

4) make imported the method that polymkeric substance that a plurality of mercaptan form and the compound with carbon-to-carbon double bond and above-mentioned adsorption site react endways in the presence of free radical generating agent;

5) in the presence of mercaptan compound, make the method for vinyl monomer generation radical polymerization with a plurality of above-mentioned adsorption sites.

In aforesaid method, the easiness on synthetic considers preferred 2), 3), 4), 5) method, more preferably 3), 4), 5) method, preferred especially 5) method.

As above-mentioned 5) method, more specifically, preferably in the presence of by the compound of following formula (3-3) expression, make the method for vinyl monomer generation radical polymerization.

In above-mentioned formula (3-3), R ⁶, R ⁷, A ³, m and n separately with above-mentioned formula (3-2) in R ³, R ⁴, A ², m and n implication identical, its preferred version is also identical.

Can synthesize with following method etc. by the compound of above-mentioned formula (3-3) expression:

6) method that converts mercaptan compound to by the halide compound with a plurality of above-mentioned adsorption sites (can be enumerated the method for the send as an envoy to reaction of above-mentioned halide compound and thiocarbamide, hydrolysis; Make the method that above-mentioned halide compound is direct and NaSH reacts; Make above-mentioned halogenide and CH ₃COSNa reacts, makes the method for its hydrolysis etc.);

7) make the compound that in a part, has 3～10 sulfydryls with have above-mentioned adsorption site and have can with the method for the compound generation addition reaction of the functional group of sulfydryl reaction.

But the easiness on synthetic considers more preferably following 7) method.

As above-mentioned 7) in the method can with the functional group of sulfydryl reaction, can preferably enumerate for example acyl halide, alkylogen, isocyanic ester, carbon-to-carbon double bond etc.

Preferred above-mentioned especially can be carbon-to-carbon double bond with the functional group of sulfydryl reaction, and addition reaction is the free radical addition reaction.In addition, as carbon-to-carbon double bond, from considering that with reactive viewpoint of sulfydryl more preferably 1 replaces or 2 vinyl that replace.

Object lesson [(18)～(34)] as the compound that has 3～10 sulfydryls in a part can list following compound.

In the object lesson ((18)～(34)) of above-claimed cpd, consider from acquired, the synthetic easiness of raw material, deliquescent viewpoint all kinds of SOLVENTS, be preferably following compound especially.

As the compound that has above-mentioned pigment adsorption structure and have a carbon-to-carbon double bond (particularly, has at least a kind that from organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, carbonatoms are alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and hydroxyl more than 4, selects, and the compound with carbon-to-carbon double bond), be not particularly limited, can preferably enumerate following compound.

The above-mentioned compound that has 3～10 sulfydryls in a part and the free radical addition reaction product that has above-mentioned pigment adsorption structure and have a compound of carbon-to-carbon double bond for example can be utilized the above-mentioned compound dissolution that has the compound of 3～10 sulfydryls and have above-mentioned pigment adsorption structure and have a carbon-to-carbon double bond in a part in The suitable solvent, to wherein adding free radical generating agent, under about 50 ℃～100 ℃, the method (mercaptan-alkene photochemical reaction method) of its addition is obtained.

As the example of the The suitable solvent of in above-mentioned mercaptan-alkene photochemical reaction method, using, can be according to the compound that in a part, has 3～10 sulfydryls that uses, have above-mentioned pigment adsorption structure and have the compound of carbon-to-carbon double bond and the solvability of the free radical addition reaction product that generates is chosen selection wantonly.

As above-mentioned solvent, for example can list methyl alcohol, ethanol, propyl alcohol, Virahol, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl-acetic acid ester, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), methoxy propyl yl acetate, ethyl lactate, vinyl acetic monomer, acetonitrile, tetrahydrofuran (THF), dimethyl formamide, chloroform, toluene.These solvents can a kind of independent use, also can be two or more and use.

As above-mentioned free radical generating agent, for example can list 2,2 '-azo two (isopropyl cyanide) (AIBN), 2,2 '-azo two-(2,4 '-methyl pentane nitrile), 2, azo-compounds such as 2 '-azo-bis-iso-dimethyl, persulphates such as superoxide of benzoyl peroxide and so on and Potassium Persulphate, ammonium persulphate etc.

As above-mentioned 5) method in the vinyl monomer that uses, be not particularly limited, for example can use with in obtaining above-mentioned formula (3-1) by P ¹Employed vinyl monomer identical vinyl monomer during the polymer backbone of expression.

Above-mentioned vinyl monomer can be only with a kind of polymerization, also can and come copolymerization with two or more.

The polymkeric substance of above-mentioned B composition can use the compound (following abbreviate as sometimes " chain-transfer agent ") of above-mentioned vinyl monomer and above-mentioned formula (3-3) expression among the present invention, with known method, according to ordinary method their polymerizations is obtained.For example, utilize these vinyl monomers of dissolving and above-mentioned chain-transfer agent in The suitable solvent,, under about 50 ℃～220 ℃, its polymeric method (solution polymerization process) in solution is obtained to wherein adding radical polymerization initiator.

As the The suitable solvent of in solution polymerization process, using, can select arbitrarily according to the solvability of the multipolymer of monomer that uses and generation, can list for example methyl alcohol, ethanol, propyl alcohol, Virahol, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl-acetic acid ester, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), methoxy propyl yl acetate, ethyl lactate, vinyl acetic monomer, acetonitrile, tetrahydrofuran (THF), dimethyl formamide, chloroform, toluene etc.These solvents can a kind of independent use, also can be two or more and use.

In addition, as radical polymerization initiator, can utilize 2,2 '-azo two (isopropyl cyanide) (AIBN), 2,2 '-azo two-(2,4 '-methyl pentane nitrile), 2, the azo-compound of 2 '-azo-bis-iso-dimethyl and so on, the superoxide of benzoyl peroxide and so on, and persulphate such as Potassium Persulphate, ammonium persulphate etc.

Among the present invention, above-mentioned (B) composition can a kind of independent use, also can be two or more and use.

As the content of above-mentioned in the ink composite of the present invention (B) composition, with respect to the add-on of above-mentioned (A) composition (pigment dyestuff), be preferably 1～100 weight %, more preferably 5～50%.

The add-on of above-mentioned (B) composition is 1 weight % when above, owing to obtained good dispersiveness, does not form particle diameter big (agglutinative) and disperses thing, so be preferred.In addition, the add-on of above-mentioned (B) composition is 100 weight % when following, rises owing to can not produce the viscosity that is caused by remaining ingredient (C) composition, so be preferred.

In addition, in the ink composite of the present invention, only otherwise damage effect of the present invention, except above-mentioned (B) composition, can also also use known pigment dispersing agent.As the content of known pigment dispersing agent this moment in above-mentioned ink composite, with respect to the add-on of above-mentioned (B) composition, be preferably below the 50 weight %, more preferably below the 30 weight %.

As known dispersion agent (pigment dispersing agent), can list macromolecule dispersing agent [for example, polyamidoamine and salt thereof, poly carboxylic acid and salt thereof, high molecular unsaturated acid ester, modified polyurethane, modified poly ester, poly-(methyl) acrylate of modification, (methyl) acrylic copolymer, naphthalene sulfonic acidformaldehyde condensation product] and polyxyethylated phosphonic acid ester, polyoxyethylene alkyl amine, alkanolamine, pigment derivative etc.

Above-mentioned macromolecule dispersing agent is considered from its structure, can also be divided into straight chain shape polymer, terminal-modified type polymer, graft type polymer, block type polymer.

Above-mentioned macromolecule dispersing agent is adsorbed on the surface of above-mentioned pigment, plays the agglutinative effect again that prevents thus.Therefore, can list terminal-modified type polymer, graft type polymer, the block type polymer that has to surface of pigments fixed position as preferred construction.On the other hand, above-mentioned pigment derivative has the effect that promotes macromolecule dispersing agent absorption by above-mentioned surface of pigments being carried out modification.

Object lesson as above-mentioned known dispersion agent (pigment dispersing agent) can list: BYKChemie corporate system " Disperbyk-101 (polyamidoamine phosphonate); 107 (carboxylicesterss); 110 (multipolymers that contain acidic group); 130 (polymeric amide); 161; 162,163,164,165,166,170 (high-molecular copolymers) "; " BYK-P104, P105 (high molecular unsaturated polyester carboxylic acid), EFKA corporate system " EFKA4047; 4050; 4010; 4165 (polyurethane series); EFKA4330; 4340 (segmented copolymers), 4400,4402 (modified polyacrylates), 5010 (polyesteramides), 5765 (high molecular polycarboxylates), 6220 (fatty acid polyesters), 6745 (phthalocyanine derivates), 6750 (azo pigment derivatives) "; system " the Ajisper PB821 of aginomoto Fine Techno Co., Ltd., PB822 "; common prosperity company chemistry corporate system " Flowren TG-710 (oligourethane) "; " Polyflow No.50E, No.300 (acrylic copolymer) "; nanmu originally changes into corporate system " DisperonKS-860,873SN, 874, #2150 (aliphatics polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725 "; KAO. Corp. SA's system " Demol RN, N (naphthalene sulfonic acid formaldehyde condensation polymer), MS, C, SN-B (aromatic sulphonic acid formaldehyde condensation products) "; " HOMOGENOL L-18 (polymeric polycarboxylic acid) "; " Emulgen 920,930,935,985 (polyoxyethylene nonylplenyl ethers) "; " Acetamine 86 (stearylamide acetic ester) "; Lubrizol corporate system " SOLSPERSE 5000 (phthalocyanine derivates), 22000 (azo pigment derivatives), 13240 (polyesteramines), 3000,17000,27000 (polymers that partly have funtion part endways), 24000,28000,32000,38500 (graft type polymers) "; daylight Chemical person corporate system " Nikol T106 (polyoxyethylene sorbitan monoleate) "; MYS-IEX (polyoxyl 40 stearate) " etc.

＜(C) active radiation-curable compound 〉

Ink composite of the present invention contain active radiation-curable compound (below be also referred to as polymerizable compound.)。Active radiation-curable compound is not particularly limited so long as produce polyreaction or crosslinking reaction and carry out the solidified compound and get final product by shining active radioactive rays, can be according to the purpose selection that suit.

No matter be that monomer, oligopolymer, polymkeric substance can use, kind produce polyreaction, a known various known polymerizable monomer as cationically photopolymerizable monomer, optical free radical polymerizable monomer but preferably utilize the polymerization that produces from polymerization starter described later to cause.

Polymerizable compound of the present invention be can be used for and addition polymerization compound, more preferably free-radical polymerised compound are preferably.In addition, can be used for polymerizable compound of the present invention and also can use the plural polymerizable compound, also preferred also with free-radical polymerised compound and cationically polymerizable compound.

Above-mentioned polymerizable compound can a kind of independent use, also can be in order to adjust purpose such as speed of response, printing ink rerum natura, cured film rerum natura and with more than two kinds.

As above-mentioned polymerizable compound, can be monofunctional compound, also can be the polyfunctional compound.

[free-radical polymerised compound]

As being used for free-radical polymerised compound of the present invention, can preferably use ethylenically unsaturated compounds.

Ethylenically unsaturated compounds be preferably selected from have at least one, the compound of two above terminal olefinic link formula unsaturated link(age)s (simple function or polyfunctional compound) more preferably.

Specifically, can from industrial field of the present invention, suit in the extensive known free-radical polymerised compound to select, comprise for example having monomer, prepolymer, i.e. the free-radical polymerised compound of dipolymer, trimer and oligopolymer or their mixture and their chemical forms such as multipolymer.

Specifically; ethylenically unsaturated compounds preferably has the compound of acryl, methacryloyl, allyl group, vinyl, internal double bonds base polymerizability bases such as (toxilic acids etc.) at intramolecularly; wherein; from considering preferably have the compound of acryl, methacryloyl with the viewpoint of low-yield generation curing reaction.

As free-radical polymerised compound, the preferred ethylenically unsaturated compounds with cyclic group that uses as cyclic group, can example illustrate aliphatics cyclic group, heterocyclic radical and fragrant cyclic group.As the aliphatics cyclic group, more preferably condense the fused polycycle base of formation more than two rings.

In addition, free-radical polymerised compound preferably has the polymerizability base of the acryloxy, methacryloxy, acrylamido, methacryloyl amido and the N-vinyl that are selected from as the ethylenic unsaturated group.

-have the ethylenically unsaturated compounds of heterocyclic radical-

Make the compound with heterocyclic radical used in this invention as suitable, can preferably list N-vinyl lactam class.

As the preferred example that can be used for N-vinyl lactam class of the present invention, can list the compound of following formula (A-1) expression.

In the formula (A-1), n represents 1～5 integer, the flexibility after solidifying from ink composite, considers that with the adhesivity and the raw-material acquired easily viewpoint of printing medium n is preferably 2～4 integer, n more preferably 2 or 4, and preferred especially n is 4 to be the N-caprolactam.The N-caprolactam is because security is good, be use always and can obtain more cheaply, can obtain good especially solidified nature and to the adhesivity of printing medium, so be preferred.

In addition, above-mentioned N-vinyl lactam class also can have substituting groups such as alkyl, aryl on lactam nucleus, can also connect saturated or unsaturated ring structure.

In addition, more preferably above-mentioned N-caprolactam.

The content of N-vinyl lactam class is preferably more than the 5 weight % of whole ink composites in the ink composite of the present invention, more preferably 5～40 weight %, more preferably 10～40 weight %.The usage quantity of N-vinyl lactam class is in above-mentioned scope the time because solidified nature, flexibility, with the adhesivity excellence of printing medium, so be preferred.

In addition, N-vinyl lactam class is the higher compound of fusing point.If the content of N-vinyl lactam class is below the 40 weight %, even if then under the low temperature below 0 ℃, also show good solubility, but the operating temperature range of ink composite broaden, so be preferred.

Above-mentioned N-vinyl lactam class can only contain a kind in ink composite, also can contain multiple.In addition, the N-vinyl lactam of use more than two kinds is as N-vinyl lactam time-like, and the total content of N-vinyl lactam class is preferably in the above-mentioned scope.

-have the ethylenically unsaturated compounds of fragrant cyclic group and have the ethylenically unsaturated compounds of aliphatics cyclic group-

The suitable free-radical polymerised compound with fragrant cyclic group that uses among the present invention is described in detail with the free-radical polymerised compound with aliphatics cyclic group.

Among the present invention,, can list the ethylenically unsaturated compounds of following formula (5 ') expression as the compound with fragrant cyclic group or aliphatics cyclic group that can suit to use.

In the above-mentioned formula (5 '), R ¹Expression hydrogen atom or methyl.

n ¹Be the integer more than 1, be preferably 1～4 integer, more preferably 1 or 2, more preferably 1.

X in the formula (5 ') ¹Expression contains the divalent linker of (C (O) O-) or (C (O) NH-) of the ethylenic unsaturated double-bond bonding that carbon atom and formula (5 ') by carbonyl represent, this divalent linker can also be further with ehter bond (O-), ester bond (C (O) O-or-OC (O)-), amido linkage (C (O) NH-or-NHC (O)-), ketonic linkage (C (O)-), can to have the ramose carbonatoms be alkylidene group below 20 or the group bonding that is combined into by them.

Above-mentioned divalent linker more preferably-C (O) O-,-C (O) NH-or-C (O) O-or-C (O) NH-and ehter bond, ester bond or carbonatoms are the group that the alkylidene group below 20, group that they are combined into more than 2 are formed by connecting.

R in the formula (5 ') ²Be the group that has the ring texture more than 1 at least, its expression: comprise the aromatic series base of monocyclic aromatic base and/or Ppolynuclear aromatic base, and the ester ring type alkyl with naphthenic hydrocarbon skeleton, diamantane skeleton and norbornane skeleton.In addition, in the ring texture of above-mentioned aromatic series base and alicyclic hydrocarbon radical, can also contain heteroatomss such as O, N, S.

As in the formula (5 ') by R ²The preferred example of the aromatic series base of expression except the phenyl as monocyclic aromatic, can also example illustrate the Ppolynuclear aromatic base with 2～4 rings.

As above-mentioned Ppolynuclear aromatic base, specifically can preferably list naphthyl, anthryl, 1H-indenyl, 9H-fluorenyl, non-that thiazolinyl of 1H-(phenalenyl), phenanthryl, three adjacent phenylenes, pyrenyl, naphthacenyl, benzo anthryl (tetraphenyl), biphenylene base, as-benzo two indenyls, s-benzo two indenyls, acenaphthylenyl, fluoranthene base, acephenanthrylenyl, aceanthrylenyl, 1,2-benzo phenanthryl, seven days of the week thiazolinyl etc.

Ethylenically unsaturated compounds with aromatic series base comprises (methyl) vinylformic acid phenoxy ethyl.

These aromatic series bases also can be to contain heteroatomic aromatic heterocycles such as O, N, S.Specifically can list monocyclic aromatic heterocycle bases such as furyl, thienyl, 1H-pyrryl, 2H-pyrryl, 1H-pyrazolyl, 1H-imidazolyl, isoxazolyl, isothiazolyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, triazolyl, tetrazyl.

In addition, can list thianthrenyl, benzofuryl, isobenzofuran-base, chromenyl, heterochromatic thiazolinyl, xanthenyl phenoxathiinyl (phenoxathiinyl), indolizinyl, pseudoindoyl, indyl, indazolyl, purine radicals, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolyl, the cinnolines base, pteridyl, carbazyl, the β-Ka Lin base, phenanthridinyl, acridyl, perimidinyl, phenanthrolinyl, phenazinyl, phenothiazinyl phenoxazinyl, pyrrolizine base Ppolynuclear aromatic heterocyclic radicals such as (pyrrolizinyl).

Halogen atom, hydroxyl, amino, sulfydryl, siloxanes, carbonatoms that above-mentioned aromatic series base can also have more than 1 or 2 are the substituting groups such as alkyl below 30.For example as phthalate anhydride or Phthalimide, 2 above substituting groups that the aromatic series base had also can form heteroatomic ring texturees such as containing O, N, S.

In addition, the R in the formula (5 ') ²It also can be the ester ring type alkyl.In addition, also can be group with heteroatomic ester ring type alkyl such as containing O, N, S.

The ester ring type alkyl also can be to have the cycloalkane of 3～12 yuan of rings or the group of the thick synthetic ring structure of these cycloalkanes more than 2.Wherein, can cyclohexyl, cyclopentyl, suberyl, isobornyl, norcamphyl, adamantyl, dicyclo amyl group, double cyclopentenyl, three ring decyls etc. be shown preference.

As the above-mentioned heteroatomic ester ring type alkyl such as O, N, S that contain, can tetrahydrofuran base, pyrrolidyl (pyrrolidinyl), pyrazolidyl, imidazolidyl, isoxazole alkyl, pyranyl, thiapyran base, isothiazole alkyl, piperidyl, piperazinyl, morpholinyl, thio-morpholinyl etc. be shown example particularly.

These ester ring type alkyl and have assorted monocyclic ester ring type alkyl be preferably can have halogen atom, hydroxyl, amino, sulfydryl, siloxanes or as the oxygen base of divalent substituent (=O), and for further to have substituent total carbon atom number be the alkyl below 30 or contain heteroatomic heterocyclic radicals such as O, N, S.

In addition, the R in the formula (5 ') ²It also can be the ester ring type alkyl that has the group of the diamantane skeleton shown in the following formula (I) or have the norbornane skeleton shown in the formula (II).

R in formula (I) or the formula (II) ³And R ⁴Represent substituting group respectively independently, can be bonded on the optional position on each ester ring type hydrocarbon structure.In addition, q R that exists ³And r R that exists ⁴Respectively can be identical, also can be different.

Q R that exists ³And r R that exists ⁴Can distinguish and be monovalence or polyvalent substituting group independently, as the monovalence substituting group, being preferably hydroxyl, replacement or unsubstituted amino, sulfydryl, siloxanes, can further having substituent total carbon atom number is alkyl or heterocyclic radical below 30, perhaps as the oxygen base of divalent substituent (=O).

R ³Replacement count q and represent 0～5 integer, in addition, R ⁴Replacement count r and represent 0～5 integer.

In addition, a carbon atom in the diamantane skeleton in the formula (I) also can use ketonic linkage (C (O)-) and/or ester bond (C (O) O-) to replace, and a carbon atom in the norbornane skeleton in the formula (II) also can use ehter bond (O-) and/or ester bond (C (O) O-) replacement.

Norbornane skeleton shown in the formula (II) also can have the cyclic hydrocarbon structures shown in the formula (III).N in the formula (III) represents cyclic hydrocarbon structures, its two ends can be substituted on the optional position of norbornane skeleton, it can be single ring architecture, it also can be polynuclear plane, in addition, as above-mentioned cyclic hydrocarbon structures, except containing the hydrocarbon key, can also contain ketonic linkage (C (O)-) and/or ester bond (C (O) O-).

As the ester ring type alkyl of above-mentioned formula (III) expression, be preferably the structure of formula (IV), formula V or formula (VI) expression.

In formula (IV), formula V and the formula (VI), R ⁵, R ⁶And R ⁷Represent substituting group respectively independently, k represents 1～6 integer, and s, t and u represent 0～5 integer respectively independently, in addition, and s R that exists ⁵, the R that exists of t ⁶And u R that exists ⁷Respectively can be identical, also can be different.

The X of formula (5 ') ¹Can be bonded on the optional position on each the ester ring type hydrocarbon structure shown in following in formula (IV), formula V or the formula (VI).

R in formula (IV), formula V or the formula (VI) ⁵, R ⁶And R ⁷Represent substituting group respectively independently, can be bonded on the optional position on following each ester ring type hydrocarbon structure of formula (IV), formula V or formula (VI).R ⁵, R ⁶And R ⁷Substituting group and the R of formula (I)～formula (III) ³And R ⁴Substituent implication identical, preferred range is also identical.

Among the present invention, as free radical polymerization monomer, can preferably list the monomer of group with ring texturees such as containing phenyl, naphthyl, anthryl, pyridyl, tetrahydrofurfuryl, piperidyl, cyclohexyl, cyclopentyl, suberyl, isobornyl, three ring decyls.

As operable free radical polymerization monomer among the present invention; can preferably list (methyl) vinylformic acid norborneol ester; (methyl) isobornyl acrylate; (methyl) cyclohexyl acrylate; (methyl) vinylformic acid ring pentyl ester; (methyl) vinylformic acid ring heptyl ester; (methyl) vinylformic acid ring monooctyl ester; (methyl) vinylformic acid ring ester in the last of the ten Heavenly stems; (methyl) vinylformic acid two ring esters in the last of the ten Heavenly stems; (methyl) vinylformic acid 3-methyl cyclohexanol ester; (methyl) vinylformic acid (4-tert-butylcyclohexyl) ester; (methyl) acryloyl morpholine; (methyl) vinylformic acid (2-benzyl) ester; (methyl) vinylformic acid phenoxy ethyl; phenoxy group glycol ether (methyl) acrylate; phenoxy group triglycol (methyl) acrylate; oxyethane (EO) modification cresols (methyl) acrylate; (methyl) tetrahydrofurfuryl acrylate; caprolactone modification tetrahydrofurfuryl alcohol acrylate; Nonylphenoxy polyoxyethylene glycol (methyl) acrylate; neopentyl glycol benzoic ether (methyl) acrylate; to cumyl phenoxy group ethylene glycol (methyl) acrylate; N-Phthalimide ethanol (methyl) acrylate; (methyl) vinylformic acid pentamethyl-piperidines ester; (methyl) vinylformic acid tetramethyl piperidine ester; N-cyclohexyl (methyl) acrylamide; N-(1; 1-dimethyl-2-phenyl) ethyl (methyl) acrylamide; N-diphenyl methyl (methyl) acrylamide; N-Phthalimide methyl (methyl) acrylamide; N-(1; 1 '-dimethyl-3-(1; 2; the 4-triazol-1-yl)) propyl group (methyl) acrylamide; 5-(methyl) acryloyl-oxy ylmethyl-5-ethyl-1,3-dioxane etc.

And then the preferred object lesson of operable free radical polymerization monomer is shown in following M-1～M-56 among the present invention.

In addition, in the part of following exemplary compounds, put down in writing hydrocarbon chain with the simple structural formula of the symbol that has omitted carbon (C) and hydrogen (H).

Free-radical polymerised compound with above-mentioned cyclic group can a kind of independent use, also can more than two kinds and use.

Ink composition for ink jet of the present invention preferably uses the ethylenically unsaturated compounds that has heterocyclic radical at least, preferably uses N-vinyl lactam class as the ethylenically unsaturated compounds with heterocyclic radical.In addition, also preferred and with having the ethylenically unsaturated compounds of aromatic nucleus base or have the ethylenically unsaturated compounds of aliphatics cyclic group, preferred and with ethylenically unsaturated compounds with heterocyclic radical, have the ethylenically unsaturated compounds of fragrant cyclic group and have the ethylenically unsaturated compounds of aliphatics cyclic group.

Ink composition for ink jet of the present invention preferably contains at least a among the compound of following formula (C-1)～(C-5) expression, more preferably contain in three different ethylenically unsaturated compounds groups of compound of the compound of compound, formula (C-2) expression of the formula of being selected from (C-1) expression and formula (C-3)～(C-5) expression at least two kinds not on the same group compounds, especially preferably contain the compound of formula (C-1) expression, the compound of formula (C-2) expression and the compound of formula (C-3)～(C-5) expression.

In addition, as the compound of formula (C-2) expression, preferred (methyl) vinylformic acid phenoxy ethyl.

A in the formula (C-1) ¹Expression forms the divalent linker of 4～8 yuan of rings with nitrogen-atoms and carbonyl, be preferably alkylidene group or be selected from alkylidene group, arylidene ,-O-and-NR '-in the group that forms of moiety combinations more than two kinds, more preferably alkylidene group or be selected from alkylidene group and arylidene in the group that forms of the moiety combinations more than two kinds, further preferred alkylidene group.Above-mentioned R ' expression hydrogen atom or monovalence substituting group.In addition, above-mentioned alkylidene group, above-mentioned arylidene also can have substituting group.

Substituting group among above-mentioned alkylidene group, above-mentioned arylidene, the above-mentioned R particularly can example illustrate as the substituent alkyl of monovalence, alkenyl, alkynyl, aryl, hydroxyl, halogen atom, replacement or unsubstituted amino, thiol group and as the oxygen base of divalent substituent (=O).

R in formula (C-2)～formula (C-5) ¹Expression hydrogen atom or methyl.

N in formula (C-2)～formula (C-5) ¹Expression 1～4 integer is preferably 1 or 2, and more preferably 1.

M in the formula (C-2) represents 0～5 integer, is preferably 0～3 integer, 0～2 integer more preferably, more preferably 0.

R in the formula (C-2) ⁸Expression halogen atom, hydroxyl, amino, sulfydryl, siloxanes, carbonatoms are the alkyl below 30.M is 2 when above, the R that exists more than 2 ⁸Can be identical or different respectively.In addition, the R more than 2 ⁸Can form and as phthalate anhydride or Phthalimide, contain heteroatomic ring texturees such as O, N, S.

A in formula (C-2)～formula (C-5) ², A ³, A ⁴And A ⁵Represent singly-bound or divalent linker respectively independently.

As above-mentioned divalent linker, being preferably carbonatoms and being alkylidene group below 20 or the ehter bond more than 1 and/or ester bond and the carbonatoms more than 1 is the group that the alkylidene group below 20 is combined to form, and more preferably carbonatoms is that alkylidene group below 20 or the ehter bond more than 1 and the carbonatoms more than 1 are the group that the alkylidene group below 20 is combined to form.

R in formula (C-3)～formula (C-5) ⁵, R ⁶And R ⁷Represent substituting group respectively independently, preferred hydroxyl, replacement or unsubstituted amino, thiol group, siloxanes or can further to have substituent total carbon atom number be alkyl or heterocyclic radical below 30.

S, t and u in formula (C-3)～formula (C-5) represent 0～5 integer respectively independently, are preferably 0～3 integer, 0～2 integer more preferably, more preferably 0.In addition, s R that exists ⁵, the R that exists of t ⁶, and u R that exists ⁷Respectively can be identical or different.In addition, for two R of same carbon atom bonded ⁵, R ⁶Perhaps R ⁷Situation, they also can be as divalent substituent the oxygen base (=O).

Among the present invention, above-mentioned free-radical polymerised compound with cyclic group is preferably more than the 10 weight % of whole ink composites, 10 weight %～90 weight % more preferably, more preferably 30 weight %～90 weight % are preferably 50 weight %～85 weight % especially.

Ethylenically unsaturated compounds with heterocyclic radical preferably contains 5～40 weight % in ink composite, more preferably contain 10～40 weight %.In addition, have the ethylenically unsaturated compounds of aliphatics cyclic group and have fragrant cyclic group the content that amounts in ink composite of ethylenically unsaturated compounds be preferably 5～90 weight %, more preferably 20～85 weight %, more preferably 40～80 weight %.

In addition, can also use following free-radical polymerised compound.

For example, the light-cured type material of reporter's optical polymerism composition in each communique such as known use Japanese kokai publication hei 7-159983 number, Japan special fair 7-31399 number, Japanese kokai publication hei 8-224982 number, Japanese kokai publication hei 10-863 number.

As the example of ethylenically unsaturated compounds that can radical polymerization, preferably using unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, iso-crotonic acid, toxilic acid, their ester and their salt, the acid anhydrides with ethylenic unsaturated group, vinyl cyanide, vinylbenzene and various unsaturated polyester, unsaturated polyether, unsaturated polyester acid amides, unsaturated urethane (methyl) acrylic monomer or prepolymer, epoxy is that monomer or prepolymer, carbamate are (methyl) acrylate such as monomer or prepolymer.

Specifically, can list (gathering) glycol monomethyl (methyl) acrylate, (gathering) ethylene glycol (methyl) acrylate ester, (gathering) ethylene glycol (methyl) acrylate ethyl ester, (gathering) ethylene glycol (methyl) acrylate phenylester, (gathering) propylene glycol list (methyl) acrylate, (gathering) propylene glycol list (methyl) acrylate phenylester, (gathering) propylene glycol (methyl) acrylate ester, (gathering) propylene glycol (methyl) acrylate ethyl ester, (gathering) propylene glycol diglycidylether vinylformic acid affixture, neopentyl glycol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) 1,4-butyleneglycol two (methyl) acrylate, (gathering) 1,4-butyleneglycol two (methyl) acrylate, the PO of dihydroxyphenyl propane (propylene oxide) affixture two (methyl) acrylate, the ethoxylation neopentylglycol diacrylate, ethoxylated neopentylglycol diacrylate, the EO of dihydroxyphenyl propane (oxyethane) affixture two (methyl) acrylate, EO modification pentaerythritol triacrylate, PO modification pentaerythritol triacrylate, EO modification tetramethylol methane tetraacrylate, PO modification tetramethylol methane tetraacrylate, EO modification Dipentaerythritol tetraacrylate, PO modification Dipentaerythritol tetraacrylate, EO modification Viscoat 295, PO modification Viscoat 295, EO modification tetramethylol methane tetraacrylate, PO modification tetramethylol methane tetraacrylate, vinylformic acid (the 2-ethyl is own) ester, the vinylformic acid n-octyl, vinylformic acid ester in the positive ninth of the ten Heavenly Stems, vinylformic acid ester in the positive last of the ten Heavenly stems, Isooctyl acrylate monomer, the positive lauryl of vinylformic acid, vinylformic acid n-tridecane ester, vinylformic acid n-hexadecane ester, vinylformic acid Octadecane ester, the different tetradecane ester of vinylformic acid, vinylformic acid isooctadecane ester, vinylformic acid (2-hydroxyl second) ester, vinylformic acid butoxy ethyl ester, tetrahydrofurfuryl acrylate, benzyl acrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the Dipentaerythritol tetraacrylate, the vinylformic acid isopentyl ester, Viscoat 295, the tetramethylol methane tetraacrylate, the oligomer ester acrylate, N hydroxymethyl acrylamide, diacetone acrylamide, acrylic acid derivatives such as epoxy acrylate; Methyl methacrylate, n-BMA, methacrylic acid (the 2-ethyl is own) ester, n octyl methacrylate, methacrylic acid ester in the positive ninth of the ten Heavenly Stems, methacrylic acid ester in the positive last of the ten Heavenly stems, Isooctyl methacrylate, the positive lauryl of methacrylic acid, methacrylic acid n-tridecane ester, methacrylic acid n-hexadecane ester, methacrylic acid Octadecane ester, allyl methacrylate(AMA), glycidyl methacrylate, benzyl methacrylate, dimethylaminoethyl methacrylate, the trimethylolethane trimethacrylate methacrylic ester, trimethylolpropane trimethacrylate, 2, methacrylic acid derivatives such as two (the 4-methacryloxy polyethoxye phenyl) propane of 2-; And glycidyl allyl ether, dially phthalate, 1,2, the derivative of allylic cpds such as 4-benzene tricarboxylic acid triallyl, 1, the 6-hexanediyl ester, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 2-ethylhexyl glycol ether acrylate, 2-hydroxyl-3-phenoxy propyl acrylate, 2-hydroxybutyl acrylate, hydroxyl trimethylacetic acid neopentylglycol diacrylate, 2-acryloxy ethylbenzene dioctyl phthalate, nonylphenol EO affixture acrylate, methoxyl group-polyethylene glycol acrylate, the tetramethylol methane triacrylate, 2-acryloxy ethyl-2-hydroxyethyl phthalic acid, dihydroxymethyl tristane diacrylate, the ethoxylation phenyl acrylate, 2-acryloxy ethyl succsinic acid, the modified glycerol triacrylate, bisphenol A diglycidyl ether vinylformic acid affixture, the modified bisphenol A diacrylate, phenoxy group-polyethylene glycol acrylate, 2-acryloxy ethyl hexahydrobenzene dioctyl phthalate, dipentaerythritol acrylate, pentaerythritol triacrylate tolylene diisocyanate carbamate prepolymer, the caprolactone modification flexible acrylic ester, vinylformic acid butoxy ethyl ester, pentaerythritol triacrylate hexamethylene diisocyanate carbamate prepolymer, vinylformic acid 2-hydroxy methacrylate, methoxyl group dipropylene glycol acrylate, two (trishydroxymethyl) propane tetraacrylate, pentaerythritol triacrylate hexamethylene diisocyanate carbamate prepolymer, more particularly, can use " linking agent handbook (frame Bridge drug Ha Application De Block ッ Network) " (1981, great achievement society) of Shanxi three volumes at the foot of the mountain, add " UVEB curing handbook (a raw material piece of writing) (the UVEB sclerosis Ha Application De Block ッ Network (raw material that rattan looks volume clearly

)) " commercially available product or free-radical polymerised or cross-linkable monomer, oligopolymer and the polymkeric substance well known in the art put down in writing in " vibrin handbook (Port リ エ ス テ Le Trees fat Ha Application De Block ッ Network) " (, the Nikkan Kogyo Shimbun in 1988) of (1985, polymer publication meeting), Rad Tech research association " application of UVEB curing technology and market (the UVEB sclerosis Ji Intraoperative ying with と city Games) " compiled 79 pages (, CMC in 1989), the flourish youth work in Long mountain etc.

These acrylic compound are compared with the polymerizable compound that can be used for the UV curable ink in the past, can reduce viscosity, obtain stable printing ink spray row property, and polymerization sensitivity, also good with the adhesivity of recording medium is so be preferred.

In addition, as free-radical polymerised compound, the also preferred vinyl ether compound that uses.Vinyl ether compound as being fit to use can list for example ethylene glycol bisthioglycolate vinyl ether, ethylene glycol one vinyl ether, diethylene glycol divinyl ether, triglycol one vinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butyleneglycol divinyl ether, hexylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl one vinyl ether, hydroxyl nonyl one vinyl ether, trimethylolpropane tris vinyl ether etc. two or trivinyl ether compound; One vinyl ether compounds such as ethyl vinyl ether, n-butyl vinyl ether, IVE, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxy butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol one vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, isopropenyl ethers-O-propylene carbonate, dodecyl vinyl, glycol ether one vinyl ether, octadecyl vinyl ether etc.

In these vinyl ether compounds, consider preferred divinyl ether compound, trivinyl ether compound, preferred especially divinyl ether compound from the viewpoint of solidified nature, adhesivity, surface hardness.Vinyl ether compound can use a kind separately, also can suit to make up more than 2 kinds to use.

Wherein, consider from the viewpoint of curing speed, preferably (methyl) esters of acrylic acid, (methyl) acrylic amide, more preferably (methyl) acrylate that 4 officials can be above, in addition, consider that from the viewpoint of the viscosity of ink composite preferably multifunctional (methyl) acrylate and simple function or 2 functional (methyl) acrylate, (methyl) acrylamide are also used.

As the content of above-mentioned polymerizable compound in above-mentioned ink composite, with respect to all solids composition of this ink composite, be preferably 50～95 weight %, more preferably 60～92 weight % are preferably 70～90 weight % especially.

[cationically polymerizable monomer]

As can be, the epoxy compounds put down in writing in each communique, vinyl ether compound, oxetane compound etc. such as can suit to enumerate for example Japanese kokai publication hei 6-9714 number, TOHKEMY 2001-31892 number, TOHKEMY 2001-40068 number, TOHKEMY 2001-55507 number, TOHKEMY 2001-310938 number, TOHKEMY 2001-310937 number, TOHKEMY 2001-220526 number as the above-mentioned cationically polymerizable monomer of above-mentioned polymerizable compound.

As above-mentioned epoxy compounds, can be monofunctional epoxy compound, also can be the multi-functional epoxy compound.

As above-mentioned monofunctional epoxy compound, for example can list phenylglycidyl ether, to tert-butyl-phenyl glycidyl ether, butyl glycidyl base ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide ring, 1,3-butadiene monoxide, 1,2-epoxy dodecane, Epicholorohydrin, 1,2-epoxy decane, Styrene oxide 98min., cyclohexene oxide, 3-methacryloxy methyl cyclohexane alkylene oxygen, 3-acryloxy methyl cyclohexane alkylene oxygen, 3-vinyl cyclohexene oxygen etc.

As above-mentioned multi-functional epoxy compound, can list for example dihydroxyphenyl propane diglycidyl ether, the Bisphenol F diglycidyl ether, bisphenol-S diglycidyl base ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolak Trees fat, the Hydrogenated Bisphenol A diglycidyl ether, A Hydrogenated Bisphenol A F diglycidyl ether, A Hydrogenated Bisphenol A S diglycidyl ether, 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3, the 4-epoxy) hexanaphthene--diox, two (3,4-epoxycyclohexyl methyl) adipic acid ester, vinyl cyclohexene oxygen, 4 vinyl epoxy cyclohexane, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester, 3,4-epoxy-6-methylcyclohexyl-3 ', 4 '-epoxy-6 '-methylcyclohexanecarboxylic acid ester, methylene radical two (3, the 4-epoxy cyclohexane), the Dicyclopentadiene (DCPD) diepoxide, two (3 of ethylene glycol, 4-epoxycyclohexyl methyl) ether, ethylene (3, the 4-epoxycyclohexane carboxylate), epoxy six hydrogen dioctyl phthalates, epoxy six hydrogen phthalandiones two-2-(ethyl hexyl) ester, 1, the 4-butanediol diglycidyl ether, 1,6-hexylene glycol diglycidyl ether, glycerine triglycidyl group ether, the trimethylolpropane tris glycidyl ether, the polyoxyethylene glycol diglycidyl ether, the polypropylene glycol diglycidyl ether class, 1,1,3-four decadiene dioxide, the limonene dioxide, 1,2,7,8-diepoxy octane, 1,2,5,6-diepoxy cyclooctane etc.

In these epoxy compoundss, consider optimization aromatic epoxy compounds, alicyclic epoxy compound, preferred especially alicyclic epoxy compound from the viewpoint of curing speed excellence.

As above-mentioned vinyl ether compound, can be the monofunctional vinyl ether compound, also can be the polyfunctional vinyl ether compound.

As above-mentioned monofunctional vinyl ether compound, can list for example methylvinylether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tert-Butyl vinyl ether, 2-ethylhexyl vinyl ether, the n-nonyl vinyl ether, the lauryl vinyl ether, cyclohexyl vinyl ether, the cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methylvinylether, benzyl vinyl ether, the dicyclopentenyl vinyl ether, 2-two cyclopentenes oxygen base ethyl vinyl ethers, the methoxy ethyl vinyl ether, the ethoxyethyl group vinyl ether, the butoxyethyl group vinyl ether, the methoxyethoxyethyl vinyl ether, the ethoxy ethoxy ethyl vinyl ether, the methoxy poly (ethylene glycol) vinyl ether, tetrahydrochysene Kang base vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethyl cyclohexyl methyl vinyl ether, Diethylene Glycol one vinyl ether, the polyoxyethylene glycol vinyl ether, the chloroethyl vinyl ether, the chlorobutyl vinyl ether, the chloroethoxy ethyl vinyl ether, the phenylethyl vinyl ether, phenoxy group polyoxyethylene glycol vinyl ether etc.

As above-mentioned polyfunctional vinyl ether compound, can list for example divinyl ethers such as ethylene glycol bisthioglycolate vinyl ether, Diethylene Glycol divinyl ether, polyoxyethylene glycol divinyl ether, propylene glycol divinyl ether, butyleneglycol divinyl ether, hexylene glycol divinyl ether, dihydroxyphenyl propane alkylene oxide divinyl ether, Bisphenol F alkylene oxide divinyl ether; The trimethylolethane trimethacrylate vinyl ether, the trimethylolpropane tris vinyl ether, two (TriMethylolPropane(TMP)) tetrem alkene ether, the glycerine trivinyl ether, tetramethylolmethane tetrem alkene ether, Dipentaerythritol five vinyl ether, Dipentaerythritol six vinyl ether, oxyethane addition trimethylolpropane tris vinyl ether, propylene oxide addition trimethylolpropane tris vinyl ether, oxyethane addition two (TriMethylolPropane(TMP)) tetrem alkene ether, propylene oxide addition two (TriMethylolPropane(TMP)) tetrem alkene ether, oxyethane addition tetramethylolmethane tetrem alkene ether, propylene oxide addition tetramethylolmethane tetrem alkene ether, oxyethane addition Dipentaerythritol six vinyl ether, polyfunctional vinyl ethers such as propylene oxide addition Dipentaerythritol six vinyl ether etc.

In these vinyl ether compounds, from solidified nature, consider with the viewpoints such as surface hardness of the image of the adhesivity of printing medium, formation, preferred two or the trivinyl ether compound, preferred especially divinyl ether compound.

Above-mentioned oxetane compound is meant the compound with trimethylene oxide ring, as its example, can preferably list the known oxetane compound of putting down in writing among TOHKEMY 2001-220526 number, TOHKEMY 2001-310937 number, TOHKEMY 2003-341217 number each public Reported.

As above-mentioned oxetane compound, among the present invention, preferably in its structure, has the compound of 1-4 trimethylene oxide ring.When using such compound, advantageously be easy to the viscosity of above-mentioned ink composite is maintained in the good scope of operability, in addition, can after curing, obtain the high adhesivity of printing ink and printing medium.

As above-mentioned oxetane compound, can be the simple function oxetane compound, also can be multifunctional oxetane compound.

As above-mentioned simple function oxetane compound, can list for example 3-ethyl-3-methylol trimethylene oxide, 3-(methyl) allyl group oxygen ylmethyl-3-ethyl trimethylene oxide, (3-ethyl-3-trimethylene oxide ylmethoxy) methylbenzene, 4-fluoro-(1-(3-ethyl-3-trimethylene oxide ylmethoxy) methyl) benzene, 4-methoxyl group-(1-(3-ethyl-3-trimethylene oxide ylmethoxy) methyl) benzene, (1-(3-ethyl-3-trimethylene oxide ylmethoxy) ethyl) phenyl ether, isobutoxy methyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, isobornyl oxygen base ethyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, isobornyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, 2-ethylhexyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, ethyl Diethylene Glycol (3-ethyl-3-trimethylene oxide ylmethyl) ether, Dicyclopentadiene (DCPD) (3-ethyl-3-trimethylene oxide ylmethyl) ether, dicyclopentenyl oxygen base ethyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, dicyclopentenyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-trimethylene oxide ylmethyl) ether, tetrabromo phenyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, 2-tetrabromo phenoxy group ethyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, tribromo phenyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, 2-tribromophenoxy ethyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, butoxyethyl group (3-ethyl-3-trimethylene oxide ylmethyl) ether, five chlorophenyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, penta-bromophenyl (3-ethyl-3-trimethylene oxide ylmethyl) ether, bornyl (3-ethyl-3-trimethylene oxide ylmethyl) ether etc.

As above-mentioned multifunctional oxetane compound, for example can list 3,7-two (3-oxetanyl)-5-oxo-nonane, 3,3 '-(1,3-(2-methene) propane two bases two (oxygen methylene radical)) two-(3-ethyl trimethylene oxide), 1,4-two ((3-ethyl-3-trimethylene oxide ylmethoxy) methyl) benzene, 1,2-two [(3-ethyl-3-trimethylene oxide ylmethoxy) methyl] ethane, 1,3-two [(3-ethyl-3-trimethylene oxide ylmethoxy) methyl] propane, ethylene glycol bisthioglycolate (3-ethyl-3-trimethylene oxide ylmethyl) ether, dicyclopentenyl two (3-ethyl-3-trimethylene oxide ylmethyl) ether, triethylene glycol two (3-ethyl-3-trimethylene oxide ylmethyl) ether, TEG two (3-ethyl-3-trimethylene oxide ylmethyl) ether, tristane two basic dimethylenes (3-ethyl-3-trimethylene oxide ylmethyl) ether, trimethylolpropane tris (3-ethyl-3-trimethylene oxide ylmethyl) ether, 1,4-two (3-ethyl-3-trimethylene oxide ylmethoxy) butane, 1,6-two (3-ethyl-3-trimethylene oxide ylmethoxy) hexane, tetramethylolmethane three (3-ethyl-3-trimethylene oxide ylmethyl) ether, tetramethylolmethane four (3-ethyl-3-trimethylene oxide ylmethyl) ether, polyoxyethylene glycol two (3-ethyl-3-trimethylene oxide ylmethyl) ether, Dipentaerythritol six (3-ethyl-3-trimethylene oxide ylmethyl) ether, Dipentaerythritol five (3-ethyl-3-trimethylene oxide ylmethyl) ether, Dipentaerythritol four (3-ethyl-3-trimethylene oxide ylmethyl) ether, caprolactone modification Dipentaerythritol six (3-ethyl-3-trimethylene oxide ylmethyl) ether, caprolactone modification Dipentaerythritol five (3-ethyl-3-trimethylene oxide ylmethyl) ether, two (TriMethylolPropane(TMP)s) four (3-ethyl-3-trimethylene oxide ylmethyl) ether, EO modified bisphenol A two (3-ethyl-3-trimethylene oxide ylmethyl) ether, PO modified bisphenol A two (3-ethyl-3-trimethylene oxide ylmethyl) ether, the modified hydrogenated dihydroxyphenyl propane two of EO (3-ethyl-3-trimethylene oxide ylmethyl) ether, the modified hydrogenated dihydroxyphenyl propane two of PO (3-ethyl-3-trimethylene oxide ylmethyl) ether, EO modified bisphenol F (3-ethyl-3-trimethylene oxide ylmethyl) ether etc.

As above-mentioned oxetane compound, in addition to these, can also suit to use the compound that describes in detail in above-mentioned TOHKEMY 2003-341217 communique, paragraph (0021)～(0084) among the present invention.

In the above-mentioned described oxetane compound, consider that from the viscosity and the adhesive viewpoint of ink composite the present invention preferably has the compound of 1～2 trimethylene oxide ring.

When using the cationically polymerizable compound in the ink composite of the present invention, above-mentioned cationically polymerizable compound can a kind of independent use, also can more than two kinds and use, but the viewpoint of the contraction when suppressing ink solidification effectively considers, preferably will at least a above-mentioned oxetane compound and be selected from least a compound and usefulness in epoxy compounds and the vinyl ether compound.

＜other composition 〉

Ink composite of the present invention can also contain suit other composition of selecting of with good grounds purpose except above-mentioned A composition～above-mentioned C composition.

As above-mentioned other composition, can list for example polymerization starter, sensitizing coloring matter, common sensitizing agent (strong sensitizing agent; Be also referred to as common sensitizing agent), resin, tensio-active agent, UV light absorber, antioxidant, fading prevents agent, spray row's stablizer, adhesivity rising agent, flow agent, matting agent etc.They can a kind of independent use, also can more than two kinds and use.

(polymerization starter)

Among the present invention, when photolytic activity lines such as use ultraviolet ray make ink solidification, contain polymerization starter.As operable radical polymerization initiator among the present invention, can use known polymerization starter, preferably use radical polymerization initiator.Operable radical polymerization initiator can use separately among the present invention, and also two or more kinds may be used.In addition, can also and use radical polymerization initiator and cationic polymerization initiators.

Operable polymerization starter is to produce the compound that the polymerization initiation is planted after absorbing external energy in the ink composite of the present invention.The external energy that is used for initiated polymerization roughly is divided into heat and active radioactive rays, uses thermal polymerization and Photoepolymerizationinitiater initiater respectively.As active radioactive rays, can gamma-rays, β ray, electron beam, ultraviolet ray, visible light, infrared rays be shown example.

-radical polymerization initiator-

As operable radical polymerization initiator among the present invention, can list (a) aromatic series ketone, (b) acylphosphanes compound, (c) aromatic series salt compound, (d) organo-peroxide, (e) thio-compounds, (f) six aryl united imidazoles, (g) ketoxime ester cpds, (h) boric acid ester compound, (i) nitrine, (j) metallocene compound, (k) active ester compound, (l) and have the compound of carbon-halogen bond and (m) alkyl ammonium compounds etc.These radical polymerization initiators can be used singly or in combination the compound of above-mentioned (a)～(m).Radical polymerization initiator among the present invention can be fit to use separately or also use more than 2 kinds.

As (a) aromatic series ketone, (b) acylphosphanes compound and (e) preferred example of thio-compounds; can list J.P.FOUASSIER J.F.RABEK (1993), the compound with benzophenone skeleton or thioxanthone skeleton of record etc. in the 77th～117 page at " RADIATION CURING IN POLYMER SCIENCE ANDTECHNOLOGY ".As preferred example; can list the α-sulfo-benzophenone cpd of Japanese Patent Publication 47-6416 communique record; the benzoin ether compound of Japanese Patent Publication 47-3981 communique record; the alpha-substitution bitter almond oil camphor compound of Japanese Patent Publication 47-22326 communique record; the benzoin derivatives of Japanese Patent Publication 47-23664 communique record; the aroyl phosphonic acid ester of Japanese kokai publication sho 57-30704 communique record; the dialkoxy benzophenone of Japanese Patent Publication 60-26483 communique record; Japanese Patent Publication 60-26403 communique; the benzoin ethers of Japanese kokai publication sho 62-81345 communique record; the special fair 1-34242 communique of Japan; No. the 4318791st, United States Patent (USP); the alpha-amino group benzophenone of European patent 0284561A1 number record; Japanese kokai publication hei 2-211452 communique record to two (dimethylamino benzoyl) benzene; the sulfo-aromatic ketone of Japanese kokai publication sho 61-194062 communique record; the acylphosphanes sulfide of the special fair 2-9597 communique record of Japan; the acylphosphanes of the special fair 2-9596 communique record of Japan; the thioxanthene ketone of Japanese Patent Publication 63-61950 communique record, the coumarins of Japanese Patent Publication 59-42864 communique record etc.

As (c) aromatic series salt compound, the element that comprises 15,16 and 17 families of periodictable is the aromatic series salt of N, P, As, Sb, Bi, O, S, Se, Te or I specifically.The salt compounded of iodine class that suitable use is for example put down in writing in No. 104143 specification sheetss of European patent, No. 4837124 specification sheetss of United States Patent (USP), Japanese kokai publication hei 2-150848 communique, the Japanese kokai publication hei 2-96514 communique; No. 370693, European patent, No. 233567, European patent, No. 297443, European patent, No. 297442, European patent, each specification sheets that No. 422570, No. 279210, European patent and European patent, No. 3902144, United States Patent (USP), No. 4933377, United States Patent (USP), No. 4760013, United States Patent (USP), the diazols of putting down in writing in each specification sheets that No. 2833827, No. 4734444, United States Patent (USP) and United States Patent (USP) (can have substituent benzene diazonium etc.), diazonium salt resin class (formaldehyde resin of diazonium diphenylamine etc.), N-alkoxy pyridines salts etc. (for example, No. 4743528 specification sheetss of United States Patent (USP), Japanese kokai publication sho 63-138345 number, Japanese kokai publication sho 63-142345 number, the compound of record specifically has 1-methoxyl group-4-phenylpyridine Tetrafluoroboric acid ester etc. in Japanese kokai publication sho 63-142346 number and Japanese Patent Publication 46-42363 number each communique etc.); And the compound of putting down in writing in Japanese Patent Publication 52-147277 number, Japanese Patent Publication 52-14278 number and Japanese Patent Publication 52-14279 number each communique.Generate free radical or acid as spike.

As (d) organo-peroxide, comprise nearly all organic compound that in molecule, has 1 above o-o bond, as its example, preferred 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 3,3 ', 4,4 '-four (tert-pentyl peroxide carbonyl) benzophenone, 3,3 ', 4,4 '-four (uncle's hexyl peroxide carbonyl) benzophenone, 3,3 ', 4,4 '-four (uncle's octyl group peroxide carbonyl) benzophenone, 3,3 ', 4,4 '-four (cumyl peroxide carbonyl) benzophenone, 3,3 ', 4,4 '-four (p-isopropyl cumyl peroxide carbonyl) benzophenone, the compound of peroxyesters such as di-t-butyl diperoxy isophthalic acid ester system.

As (f) six aryl united imidazoles, can list Japanese Patent Publication 45-37377 communique, the lophine dimer class of Japanese Patent Publication 44-86516 communique record, for example 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (o-bromophenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (neighbours, right-dichlorophenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four (m-methoxyphenyl) bisglyoxaline, 2,2 '-two (o, o '-dichlorophenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (ortho-nitrophenyl bases)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (o-methyl-phenyl-)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline, 2,2 '-two (adjacent trifluorophenyls)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline etc.

As (g) ketoxime ester cpds, can list 3-benzoyloxy imino-butane-2-ketone, 3-acetoxyl group imino-butane-2-ketone, 3-propionyloxy imino-butane-2-ketone, 2-acetoxyl group imino-pentane-3-ketone, 2-acetoxyl group imino--1-phenyl-propane-1-ketone, 2-benzoyloxy imino--1-phenyl-propane-1-ketone, 3-tolysulfonyl oxygen base imino-butane-2-ketone, 2-oxyethyl group carbonyl oxygen base imino--1-phenyl-propane-1-ketone etc.

As the example of (h) boric acid ester compound, the compound of putting down in writing in can list United States Patent (USP) No. 3567453, each specification sheets of No. 4343891, United States Patent (USP), No. 109772, European patent, No. 109773, European patent.

As the example of (i) triazo-compound, can list the compound group of putting down in writing in Japanese kokai publication sho 63-138345 number, Japanese kokai publication sho 63-142345 number, Japanese kokai publication sho 63-142346 number, Japanese kokai publication sho 63-143537 number and Japanese Patent Publication 46-42363 number each communique with N-O key.

As the example of (j) metallocene compound, can list two cyclopentadiene titanium compounds of Japanese kokai publication sho 59-152396 number, Japanese kokai publication sho 61-151197 number, Japanese kokai publication sho 63-41484 number, Japanese kokai publication hei 2-249 number, Japanese kokai publication hei 2-4705 number record; And iron-aromatic hydrocarbons complex compound of putting down in writing in Japanese kokai publication hei 1-304453 number, Japanese kokai publication hei 1-152109 number each communique.

Object lesson as above-mentioned two cyclopentadiene titanium compounds; can list titanocene dichloride; dicyclopentadienyl phenylbenzene titanium; dicyclopentadienyl-titanium-two (2; 3; 4; 5; 6-penta fluoro benzene-1-yl); dicyclopentadienyl-titanium-two (2,3,5; 6-tetra fluoro benzene-1-yl); dicyclopentadienyl-titanium-two (2; 4,6-trifluoro-benzene-1-yl); dicyclopentadienyl-titanium-two (2,6-two fluorobenzene-1-yl); dicyclopentadienyl-titanium-two (2; 4-two fluorobenzene-1-yl); two (methyl cyclopentadienyl)-titaniums-two (2; 3,4,5; 6-penta fluoro benzene-1-yl); two (methyl cyclopentadienyl)-titaniums-two (2; 3,5,6-tetra fluoro benzene-1-yl); two (methyl cyclopentadienyl)-titaniums-two (2; 4-two fluorobenzene-1-yl); two (cyclopentadienyl)-two (2; 6-two fluoro-3-(pyrroles-1-yl) phenyl) titanium; two (cyclopentadienyls) two [2,6-two fluoro-3-(sulfonyloxy methyl amido) phenyl] titanium; two (cyclopentadienyls) two [2,6-two fluoro-3-(N-butyl two aroylamino) phenyl] titanium etc.

As the example of (k) active ester compound, the nitrobenzyl ester cpds of putting down in writing in each specification sheets that No. 4181531, each specification sheets that No. 0388343, can list European patent No. 0290750, European patent 046083, No. 156153, European patent, No. 271851, European patent and European patent, United States Patent (USP) 3901710 and United States Patent (USP), Japanese kokai publication sho 60-198538 number and Japanese kokai publication sho 53-133022 number each communique; The imino-sulfonate compound of putting down in writing in each specification sheets of No. 4371605, No. 4618564, each specification sheets, United States Patent (USP), the United States Patent (USP) that No. 0101122, No. 0199672, European patent, No. 84515, European patent, No. 199672, European patent, No. 044115, European patent and European patent and No. 4431774, Japanese kokai publication sho 64-18143 number, Japanese kokai publication hei 2-245756 number and Japanese kokai publication hei 4-365048 number each communique; Compound of putting down in writing in Japanese Patent Publication 62-6223 number, Japanese Patent Publication 63-14340 number and Japanese kokai publication sho 59-174831 number each communique etc.

The preferred example that has the compound of carbon-halogen bond as (l), for example can list if the Bull.Chem.Soc.Japan of Lin Dengzhu, the compound of putting down in writing in No. 3337024 specification sheetss of compound, German Patent of putting down in writing in the compound of putting down in writing in No. 1388492 specification sheetss of compound, English Patent of record in 42,2924 (1969), the Japanese kokai publication sho 53-133428 communique etc.

In addition, can list F.C.Schaefer etc., the compounds of record, the compound of Japanese kokai publication sho 62-58241 communique record, the compound of Japanese kokai publication hei 5-281728 communique record etc. in 29,1527 (1964) at J.Org.Chem..Can also list the compound group of record in No. the 3021599th, the compound group of No. 3021590 record of compound, German Patent of record in No. the 3333450th, compound, the German Patent of record in No. the 2641100th, the German Patent or the German Patent etc.

-cationic polymerization initiators-

In ink composite of the present invention, and during, preferred and use cationic polymerization initiators with the cationically polymerizable compound.

The first, can list diazonium, ammonium, iodine, sulfonium, etc. the B (C of aromatics ₆F ₅) ₄ ^-, PF ₆ ^-, AsF ₆ ^-, SbF ₆ ^-, CF ₃SO ₃ ^-Salt.The second, can list the sulfonated bodies that produces sulfonic acid.The 3rd, can also make and use up the halogenide that produces hydrogen halide.The 4th, can enumerate and tap a blast furnace-the aromatic hydrocarbons complex compound.

In ink composite of the present invention, total usage quantity of polymerization starter is preferably 0.01～35 weight % with respect to total usage quantity of polymerizable monomer, more preferably 0.5～20 weight %, the more preferably scope of 1.0～15 weight %.If be more than the 0.01 weight %, ink composite is fully solidified, if be below the 35 weight %, then can access the uniform cured film of degree of cure, so be preferred.

In addition, when in ink composite of the present invention, using sensitizing coloring matter described later, total usage quantity of polymerization starter is with respect to sensitizing coloring matter, in polymerization starter: the weight ratio of sensitizing coloring matter is preferably 200:1～1:200, more preferably 50:1～1:50, the more preferably scope of 20:1～1:5.

＜sensitizing coloring matter 〉

In ink composite of the present invention, particularly ought be used for the ink-vapor recording time spent, in order to promote to absorb the decomposition of above-mentioned polymerization starter behind the specific active radioactive rays, also can add sensitizing coloring matter.Sensitizing coloring matter absorbs specific active radioactive rays and becomes the electron excitation state.The sensitizing coloring matter that becomes the electron excitation state contacts with polymerization starter and produces effects such as transfer transport, energy transfer, heat release.Polymerization starter generation chemical transformation and decomposing generates free radical, acid or alkali thus.

As the example of preferred sensitizing coloring matter, can list compounds that belongs to following and the compound that has absorbing wavelength in 350nm to 450nm zone.

The polynuclear aromatic same clan (for example Bi, perylene, three adjacent inferior benzene), xanthene class are (for example, fluorescein, Yihong, tetraiodofluorescein, rhodamine B, rose-red), the cyanines class (for example, thiophene carbon Jing, Evil carbon cyanines), portion (for example spends the cyanines class, portion spends cyanines, carbon portion to spend cyanines), thiazides (for example, thionine, methylene blue, toluidine blue), acridine (for example, acridine orange, chloroflavin, trypaflavine), the anthraquinone class (for example, anthraquinone), square acids (for example, squaric acid), coumarins (for example, 7-diethylamino-4-methylcoumarin).

As the example of preferred sensitizing coloring matter, can list the compound of following formula (IX)～(XIII) expression.

In the formula (IX), A ¹Expression sulphur atom or NR ⁵⁰, R ⁵⁰The expression carbonatoms is that 1～8 alkyl or carbonatoms are 6～15 aryl, L ²The expression with in abutting connection with A ¹Form the nonmetallic atom group of the alkalescence nuclear of pigment, R jointly with adjoining carbons ⁵¹, R ⁵²Represent hydrogen atom or monovalence nonmetallic atom group respectively independently, R ⁵¹, R ⁵²Also can mutually combine and form the acid core of pigment.W represents Sauerstoffatom or sulphur atom.

In the formula (X), Ar ¹, Ar ²Represent independently that respectively carbonatoms is 6～15 aryl, by by-L ³The key of-formation connects.Here, L ³Expression-O-or-S-.In addition, the implication of W is identical with the implication shown in the formula (IX).

In the formula (XI), A ₂Expression sulphur atom or NR ⁵⁹, L ⁴The expression with in abutting connection with A ₂Form the nonmetallic atom group of the alkalescence nuclear of pigment, R jointly with carbon atom ⁵³, R ⁵⁴, R ⁵⁵, R ⁵⁶, R ⁵⁷And R ⁵⁸Represent monovalence nonmetallic atom group, R respectively independently ⁵⁹The expression carbonatoms is that 1～8 alkyl or carbonatoms are 6～15 aryl.

In the formula (XII), A ³, A ⁴Respectively independently expression-S-,-NR ⁶²-or-NR ⁶³-, R ⁶², R ⁶³Expression replaces or unsubstituted carbonatoms is that 1～8 alkyl, replacement or unsubstituted carbonatoms are 6～15 aryl, L independently respectively ⁵, L ⁶Respectively independently expression with in abutting connection with A ³, A ⁴Form the nonmetallic atom group of the alkalescence nuclear of pigment, R jointly with adjoining carbons ⁶⁰, R ⁶¹Represent hydrogen atom or monovalence nonmetallic atom group or bonding and form the ring of aliphatics or aromatic series mutually respectively independently.

In the formula (XIII), R ⁶⁶Expression can have substituent aromatic ring or heterocycle, A ⁵Expression Sauerstoffatom, sulphur atom or=NR ⁶⁷R ⁶⁴, R ⁶⁵And R ⁶⁷Represent hydrogen atom or monovalence nonmetallic atom group respectively independently, R ⁶⁷And R ⁶⁴, and R ⁶⁵And R ⁶⁷Bonding and form the ring of aliphatics or aromatic series mutually respectively.

Preferred object lesson as the compound of formula (IX)～(XIII) expression can list (E-1)～(E-20) shown below.

In addition, in the part of following exemplary compounds, put down in writing hydrocarbon chain with the simple structural formula of the symbol that has omitted carbon (C) and hydrogen (H).

The content of the sensitizing coloring matter in the ink composite of the present invention suits to select according to application target, in general, is preferably 0.05～4 weight % with respect to the weight of whole ink composites.

[sensitizing agent (strong sensitizing agent) altogether]

Ink composite of the present invention also preferably contains common sensitizing agent.Among the present invention, altogether sensitizing agent has further raising sensitizing coloring matter to the sensitivity of active radioactive rays or suppress the effects such as polymerization obstruction of oxygen to polymerizable compound.

Example as so common sensitizing agent; can list amine; for example in 3173 pages (1972) of " the Journal of Polymer Society " of works such as M.R.Sander the 10th volume; Japanese Patent Publication 44-20189 communique; Japanese kokai publication sho 51-82102 communique; Japanese kokai publication sho 52-134692 communique; Japanese kokai publication sho 59-138205 communique; Japanese kokai publication sho 60-84305 communique; Japanese kokai publication sho 62-18537 communique; Japanese kokai publication sho 64-33104 communique; the compounds of Research Disclosure33825 number record etc. specifically can list trolamine; the ESCAROL 507 ethyl ester; to the formyl radical xylidine; to methyl sulfo-xylidine etc.

As other example that is total to sensitizing agent, can list mercaptan, sulfide-based, the mercaptan compound of Japanese kokai publication sho 53-702 communique, Japanese Patent Publication 55-500806 communique, the record of Japanese kokai publication hei 5-142772 communique for example, the disulfides of Japanese kokai publication sho 56-75643 communique etc. specifically can list 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H) quinazoline, β-mercaptonaphthalene etc.

In addition, as other example, (for example can list amino-acid compound, N-phenylglycines etc.), the organometallic compound of Japanese Patent Publication 48-42965 communique record (for example, tributyl tin acetate etc.), the Si-H of the phosphorus compound (phosphonous acid diethyl ester etc.) of the sulphur compound of the hydrogen donor of Japanese Patent Publication 55-34414 communique record, the record of Japanese kokai publication hei 6-308727 communique (for example, trithian etc.), the record of Japanese kokai publication hei 6-250387 communique, Japanese kokai publication hei 8-54735 number record, Ge-H compound etc.

The content of the common sensitizing agent in the ink composite of the present invention suits to select according to application target, but is preferably 0.05～4 weight % with respect to the weight of whole ink composites.

[tensio-active agent]

In ink composite of the present invention,, can also add tensio-active agent in order to give long-time stable spray row property.

As tensio-active agent, can list the tensio-active agent of putting down in writing in Japanese kokai publication sho 62-173463 number, Japanese kokai publication sho 62-183457 number each communique.For example can list cationic surfactants such as nonionic surfactants such as anionic surfactants such as dialkyl sulfosuccinates class, alkyl naphthalene sulfonic acid salt, fatty acid salt, Voranol EP 2001 class, polyxyethylated allyl ether series, acetylenediol class, polyoxyethylene/polyoxypropylene block copolymers class, alkylamine salt, quaternary ammonium salt.In addition, also can use organofluorine compound to replace above-mentioned tensio-active agent.Above-mentioned organofluorine compound is preferably hydrophobic.As above-mentioned organofluorine compound, those compounds that for example comprise fluorochemical surfactant, oily fluorochemicals (for example containing fluorocarbon oil) and solid state fluorine cpd resin (for example tetrafluoroethylene resin), can list out Japanese Patent Publication 57-9053 number (the 8th～17 hurdle), put down in writing in Japanese kokai publication sho 62-135826 number each communique.

The content of the tensio-active agent in the ink composite of the present invention suits to select according to application target, but is preferably 0.00001～1 weight % with respect to the weight of whole ink composites.

＜UV light absorber 〉

Among the present invention, from the weathering resistance that improves resulting image, prevent that the viewpoint of fading from considering, can use UV light absorber.

As UV light absorber, can list the benzotriazole based compound of putting down in writing in for example Japanese kokai publication sho 58-185677 communique, Japanese kokai publication sho 61-190537 communique, Japanese kokai publication hei 2-782 communique, Japanese kokai publication hei 5-197075 communique, the Japanese kokai publication hei 9-34057 communique; The benzophenone based compound of record in No. the 3214463rd, the Japanese kokai publication sho 46-2784 communique, Japanese kokai publication hei 5-194483 communique, United States Patent (USP) etc.; The styracin based compound of record in Japanese Patent Publication 48-30492 communique, Japanese Patent Publication 56-21141 communique, the Japanese kokai publication hei 10-88106 communique etc.; The triazine based compound of record in Japanese kokai publication hei 4-298503 communique, Japanese kokai publication hei 8-53427 communique, Japanese kokai publication hei 8-239368 communique, Japanese kokai publication hei 10-182621 communique, the flat 8-501291 communique of Japanese Unexamined Patent Application Publication etc.; The compound of record among Research Disclosure No.24239 number; And to produce the compound of fluorescence, so-called white dyes etc. after the absorption ultraviolet ray that stilbene is, the benzoxazole based compound is representative.

Addition suits to select according to purpose, but is preferably 0.5～15 weight % in the solids component conversion.

＜antioxidant 〉

In order to improve the stability of ink composite, can add antioxidant.As antioxidant, can list No. 223739 communique of European publication, No. 309401 communique of Europe publication, No. 309402 communique of Europe publication, No. 310551 communique of Europe publication, No. 310552 communique of Europe publication, No. 459416 communique of Europe publication, No. 3435443 communique of Germany's publication, Japanese kokai publication sho 54-48535 communique, Japanese kokai publication sho 62-262047 communique, Japanese kokai publication sho 63-113536 communique, Japanese kokai publication sho 63-163351 communique, Japanese kokai publication hei 2-262654 communique, Japanese kokai publication hei 2-71262 communique, Japanese kokai publication hei 3-121449 communique, Japanese kokai publication hei 5-61166 communique, Japanese kokai publication hei 5-119449 communique, No. 4814262 specification sheets of United States Patent (USP), those compounds of record in No. 4980275 specification sheets of United States Patent (USP) etc.

Addition suits to select according to specific purposes, but is preferably 0.1～8 weight % in the solids component conversion.

＜fading prevents agent 〉

Can use fading of various organic systems and metal complex system to prevent agent in the ink composite of the present invention.Prevent agent as fading of above-mentioned organic system, can list hydroquinones, alkoxy benzene phenols, dialkoxy phenol, phenol, phenyl amines, amine, indenes class, chroman class, alkoxyl aniline, heterocyclic etc.Prevent agent as fading of above-mentioned metal complex system, can list nickel complex, zinc complex etc., specifically can use the compound that comprises in the general formula of the typical compound of record in the compound put down in writing in the patent of quoting in I～J item at the VII of Research Disclosure No.17643, No.15162, No.18716 650 pages of left hurdles, No.36544 527 pages, 872 pages of No.307105, No.15162, Japanese kokai publication sho 62-215272 communique 127～137 pages and the examples of compounds..

Addition suits to select according to purpose, but is preferably 0.1～8 weight % in the solids component conversion.

＜electroconductibility salt 〉

In ink composite of the present invention,, can add electroconductibility salts such as potassium sulfocyanate, lithium nitrate, ammonium thiocyanate, dimethyl amine hydrochloride in order to control spray row performance.

＜solvent 〉

In ink composite of the present invention, in order to improve the adhesivity with printing medium, the organic solvent that adds denier also is effective.

As solvent, can list for example glycol ethers series solvents such as ether series solvent, glycol monomethyl methyl ether, ethylene glycol dimethyl ether such as ester series solvents such as aromatic solvents such as chlorine series solvent, benzene, toluene, vinyl acetic monomer, N-BUTYL ACETATE, Iso Butyl Acetates such as pure series solvent, chloroform, methylene dichloride such as ketone series solvents such as acetone, methylethylketone, metacetone, methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, 1-butanols, the trimethyl carbinol, diethyl ether, tetrahydrofuran (THF), diox etc.

At this moment, adding in the scope of the problem that can not cause solvent resistance or VOC is that effectively its amount is preferably 0.1～5 weight % with respect to whole ink composites, more preferably 0.1～3 weight %.

＜macromolecular compound 〉

In ink composite of the present invention,, can add various macromolecular compounds in order to adjust film properties.As macromolecular compound, can use acrylic acid polymer, polyvinyl butyral resin, urethane resin, polyamide resin, vibrin, Resins, epoxy, phenolic resin, polycarbonate resin, polyvinyl butyral resin, vinyl-formal resin, lac, vinyl resin, acrylic resin, rubber is resin, wax class, other natural resin etc.In addition, also can and with in them more than 2 kinds.Wherein, the preferred vinyl based copolymer that obtains of the copolymerization by acrylic monomer.And then, form the also preferred multipolymer that uses " containing carboxylic monomer ", " alkyl methacrylate " or " alkyl acrylate " as structural unit as the copolymerization of macromolecular compound.

In addition, can also contain as required for example levelling additive, matting agent, be used to adjust film properties the wax class, be used to improve with the adhesivity of printing mediums such as polyolefine or PET and can not hinder polymeric tackifier etc.

As tackifier, specifically can list 5～6 pages of records of TOHKEMY 2001-49200 communique high-molecular weight adhesivity polymkeric substance (for example, by (methyl) vinylformic acid and to have carbonatoms be that ester, (methyl) vinylformic acid and the carbonatoms of the alcohol of 1～20 alkyl is that ester, (methyl) vinylformic acid and the carbonatoms of 3～14 alicyclic alcohol is the multipolymer that the ester of 6～14 aromatic alcohols constitutes), have the lower molecular weight tackifying resin of polymerizability unsaturated link(age) etc.

＜printing ink rerum natura 〉

Among the present invention, consider spray row property, preferably use 25 ℃ viscosity to be the ink composite below the 50mPas, 3～50mPas more preferably, more preferably 5～40mPas is preferably 7～30mPas especially.In addition, the viscosity of spray row's temperature (be 25～80 ℃ for example, be preferably 25～50 ℃) is preferably 3～15mPas, more preferably 3～13mPas.Ink composite of the present invention is preferably adjusted suitable ratio of components so that viscosity is above-mentioned scope.By setting the viscosity under the room temperature higher, even when using the printing medium of porous matter, also can avoid ink composite to be penetrated in the printing medium, can reduce uncured monomer, reduce stink.And then the oozing of printing ink can suppress the droplet of ink inking time swim, and resultant image quality improves, thereby is preferred.

In addition, above-mentioned viscosity is used for example cone-plate type rotational viscosimeter (E type viscometer) or Brookfield LVDV-I measurements such as (Brookfield viscometer, Brookfield corporate systems).

25 ℃ surface tension of ink composite of the present invention is preferably 20～35mN/m, more preferably 23～33mN/m.When on various printing mediums such as polyolefine, PET, White Board, uncoated paper, writing down, consider from oozing the viewpoint of spreading and sinking in and permeating, be preferably more than the 20mN/m, consider from the viewpoint of wettability, be preferably below the 35mN/m.

In addition, above-mentioned surface tension for example can use the tensiometer of Wilhelmy method or the tensiometer of DuNouy to measure.

＜make

The manufacture method of ink composite of the present invention is not particularly limited, and can suit to select according to purpose, for example, can make by above-mentioned each composition is mixed.In addition, above-mentioned mixing can use known mixing tank to carry out according to known method.

＜use

Ink composite of the present invention can suit can suit especially as composition for ink jet recording as the various printing ink that are used for image recording.At this moment, with this ink composite by printing of inkjet printer on printing medium, then, go up the above-mentioned active radioactive rays of irradiation at the ink composite of printing (document image), it is solidified carries out image recording.

Use the image recording article (print) that ink composite of the present invention obtains owing to be by being cured, so the excellent strength of image portion to above-mentioned active radioactive rays such as image portion irradiation ultraviolet radiations.Therefore, except image recording (image formation), can also be applicable to for example various uses such as formation of the ink receiving layer of lithographic plate (image portion).

(ink jet recording method and ink-jet recording device)

Ink composite of the present invention is used as ink-vapor recording.

Ink jet recording method of the present invention is following method: ink composite of the present invention spray is discharged on the printing medium (supporter, recording materials etc.) is used for ink-vapor recording, the ink composite that spray is discharged on the printing medium shines active radioactive rays, and ink composite is solidified to form image.

More specifically, ink jet recording method of the present invention is characterised in that it contains following operation: (a ¹) ink composite of the present invention is sprayed the operation that is discharged on the printing medium, and (b ¹) spray row's ink composite is shone active radioactive rays, thus make this ink composite solidified operation.

Ink jet recording method of the present invention is owing to contain above-mentioned (a ¹) and (b ¹) operation, so form image by solidified ink composite on printing medium.

(a in the ink jet recording method of the present invention ¹) can use the ink-jet recording device of following detailed description in the operation.

＜ink-jet recording device 〉

Ink-jet recording device as using in the ink jet recording method of the present invention is not particularly limited, and the known ink-jet recording device that can select arbitrarily to realize target resolution uses.That is,, all can implement (a of ink jet recording method of the present invention so long as comprise the known ink-jet recording device of commercially available product ¹) the printing ink spray is discharged on the printing medium in the operation.

As operable ink-jet recording device among the present invention, can list and comprise for example device of ink supply system, temperature sensor, active radiation source.

Ink supply system for example comprises main jar, supplying tubing, inking jar, strainer, the piezo-electric type ink gun in front of ink gun that contains ink composite of the present invention.Can drive the piezo-electric type ink gun, make its can be preferably 320 * 320～4000 * 4000dpi, more preferably 400 * 400～1600 * 1600dpi, more preferably the resolving power spray row of 720 * 720dpi is preferably 1～100pl, the multiple size ink dot (multisize dot) of 8～30pl more preferably.In addition, said dpi represents counting of every 2.54cm among the present invention.

As mentioned above, the radiation-curing type printing ink as ink composite of the present invention is set at steady temperature owing to preferably will spray row's printing ink, and therefore part can be carried out thermal insulation or heating from the inking jar to ink gun.As temperature-controlled process, be not particularly limited, but preference adds thermal control as on each pipe arrangement position a plurality of temperature sensors being set according to printing ink flow, envrionment temperature.Temperature sensor can be arranged near the nozzle of inking jar and ink gun.In addition, the head unit of heating is preferably by thermoshield or thermal insulation, so that apparatus main body can not be subjected to the temperature effect of extraneous air.To heat required printer start time in order shortening,,, to reduce the thermal capacity of whole heating unit simultaneously preferably with head unit and other position thermal insulation perhaps in order to reduce the loss of heat energy.

When using above-mentioned ink-jet recording device spray row ink composite of the present invention, preferably, ink composite is heated to is preferably 25～80 ℃, more preferably 25～50 ℃, thereby make viscosity drop to the 3～15mPas of ink composite, carry out after being preferably 3～13mPas.Particularly,, then can spray row well, thereby be preferred if use 25 ℃ viscosity to be the ink composite below the 50mPas as ink composite of the present invention.By using this method, can realize high spray row stability.

Radiation-curing type ink composite as ink composite of the present invention is because generally than the viscosity height of the water color ink that uses in the common composition for ink jet recording, so the viscosity change that the temperature variation during spray row causes is big.The viscosity change of printing ink can produce big influence to the variation of drop size and the variation of drop spray row speed, even can cause deterioration in image quality.The temperature of the printing ink in the time of therefore, spray must being arranged remains constant as far as possible.Therefore, among the present invention, the temperature span of control limit of control of printing ink be preferably design temperature ± 5 ℃, more preferably design temperature ± 2 ℃, more preferably design temperature ± 1 ℃.

Below to (b ¹) spray row's ink composite is shone active radioactive rays, thus this ink composite solidified operation is described.

The ink composite that spray is discharged on the printing medium solidifies by shining active radioactive rays.This be since in the ink composite of the present invention the polymerization starter that contains decompose because of the irradiation of active radioactive rays, produce free radical, acid, alkali etc. and cause kind, this initiations is planted and is played a role and cause and promote the polyreaction of free-radical polymerised compound.At this moment, in ink composite, if having sensitizing coloring matter with polymerization starter, then the sensitizing coloring matter assimilating activity radioactive rays in the system become excited state, by contact the decomposition that promotes polymerization starter with polymerization starter, can realize the more curing reaction of high sensitivity.

Here, employed active radioactive rays can use alpha-ray, gamma-rays, electron beam, X ray, ultraviolet ray, visible light or infrared rays etc.Although the peak wavelength of active radioactive rays also depends on the absorption characteristic of sensitizing coloring matter, for example be preferably 200～600nm, more preferably 300～450nm, more preferably 350～420nm.

In addition, even if the polymerization initiation system of ink composite of the present invention is the system that also has sufficient sensitivity with lower powered active radioactive rays.Therefore, plane of exposure illumination is preferably 10～4000mW/cm ², 20～2500mW/cm more preferably ²Its curing is suited.

As active radiation source, mainly utilize mercury lamp or gas/solid laser etc., as the solidified light source that is used for ultraviolet photo-curing type composition for ink jet recording, mercury lamp, metal halide lamp are known to widely.But, consider that from the viewpoint of present environment protection wish mercurylessly strongly, replacing to GaN based semiconductor ultra-violet light-emitting equipment all is being very useful on the industry, on the environment.And then the volume of LED (UV-LED), LD (UV-LD) is little, the life-span is long, efficient is high, cost is low, and ink-jet is expected with light source as light-cured type.

In addition, photodiode (LED) and laser diode (LD) can be used as active radiation source use.When particularly needing ultraviolet source, can use ultraviolet LED and ultraviolet LD.For example, Ri Ya KCC sells the purple LED with main emmission spectrum wavelength between 365nm and 420nm.When needing more the short wavelength, but the LED that emission wavelength concentrates on the active radioactive rays between 300nm and the 370nm is disclosed in No. 6084250 specification sheets of U.S. Patent number.In addition, other ultraviolet LED also can obtain, and can shine the radiation of different ultraviolet bandwidth.Particularly preferred active radiation source is UV-LED among the present invention, particularly preferably is the UV-LED that has peak wavelength at 350～420nm.

In addition, the highest illumination of LED on printing medium is preferably 10～2000mW/cm ², 20～1000mW/cm more preferably ², be preferably 50～800mW/cm especially ²

Ink composite of the present invention is preferably used above-mentioned active radiation exposure 0.01～120 second, more preferably 0.1～90 second.

The illuminate condition and the basic illuminating method of active radioactive rays are disclosed in the Japanese kokai publication sho 60-132767 communique.Particularly, light source is set, by the mode of shuttling back and forth with what is called head unit and light source is scanned and carry out in the both sides of the head unit of the spray arranging device that comprises printing ink.The irradiation of active radioactive rays is to carry out through (for example being 0.01～0.5 second, more preferably 0.01～0.3 second, more preferably 0.01～0.15 second) behind the certain hour after the printing ink inking.Like this by beginning to be controlled at the utmost point in the short period of time, can prevent from that printing ink in inking on the printing medium from oozing to spread and sink in before curing from the printing ink inking to the time of irradiation.In addition, even if owing to the printing medium for porous matter, printing ink also can infiltrate into the deep prior exposure that light source can not arrive, so can suppress the residual of unreacted monomer, the result has reduced stink, thereby is preferred.

And then, also can be with finishing curing without another light source that drives.Disclose in the WO99/54415 brochure in the world, as illuminating method, the method of using optical fiber is disclosed and will calibrate after light source be incident to minute surface in the setting of head unit side, thereby to the method for the irradiation UV of record portion light, above-mentioned curing also goes for ink jet recording method of the present invention.

By adopting above-mentioned ink jet recording method, even if for the different various printing mediums of surface moist, also the point of the printing ink of inking directly can be remained constantly, picture quality improves.In addition, in order to obtain coloured image, preferably the color from low lightness begins to superpose successively.Begin to superpose successively by the printing ink from low lightness, illuminated line arrives the printing ink of bottom easily, can expect to solidify that sensitivity is good, residual monomer reduces, stink reduces, adhesivity improves.In addition, irradiation can be carried out total exposure after the whole colors of spray row, but from promoting the solidified viewpoint to consider, preferred per a kind of color is carried out single exposure.

So, when ink composite of the present invention is cured by shining active radioactive rays, can on the printing medium surface, form image with coming high sensitivity.

＜printing medium 〉

Come the printing medium of document image as spray row above-mentioned ink composite of the present invention, be not particularly limited, can suit to select according to purpose, can list stationeries such as common uncoated paper, White Board, so-calledly be used for the various nonabsorbable resin materials of soft packaging or make its resin film that is configured as film like etc.In addition, as above-mentioned resin film, can list for example PET film, OPS film, OPP film, ONy film, PVC film, PE film, TAC film, polycarbonate film, acylate film, ABS film, poly-acetal film, PVA film, rubber-like film etc.In addition, as above-mentioned printing medium, also can use metal species, category of glass etc.

(print)

Print of the present invention solidifies above-mentioned ink composite of the present invention and obtains, and as this print, preferably spray row above-mentioned ink composite of the present invention on above-mentioned printing medium is solidified to form it.At this moment, above-mentioned spray row is undertaken by the ink-vapor recording that uses ink-jet printer.

Print of the present invention is owing to the ink composite that is used for image recording is an above-mentioned ink composite of the present invention, and evenly and stably disperse to contain trickle pigment particles, so color developing, boldness excellence, the figure image height, weathering resistance is also excellent, can use aptly in extensive fields.

Embodiment

Below embodiment is shown and comparative example is described more specifically the present invention.But, the present invention is not subjected to the qualification of these embodiment.

In addition, " part " in below putting down in writing, short of specializing just represented " weight part ".

The material that uses among the present invention is as described below.

HEUCO GREEN 600703K (C.I. pigment Green 7); The Heubach corporate system

Monastral GREEN GN-C (C.I. pigment Green 7); The Heubach corporate system

Monastral GREEN GNX-C (C.I. pigment Green 7); The Heubach corporate system

Monastral GREEN GBX-C (C.I. pigment Green 7); The Heubach corporate system

HOSTAPERM GREEN GG01 (C.I. pigment Green 7); The Clariant corporate system

HOSTAPERM GREEN GNX-D (C.I. pigment Green 7); The Clariant corporate system

HOSTAPERM GREEN GNX-TS (C.I. pigment Green 7); The Clariant corporate system

PV Fast GREEN GNX (C.I. pigment Green 7); The Clariant corporate system

Novotex GREEN GNX (C.I. pigment Green 7); The Clariant corporate system

Fastogen GREEN S (C.I. pigment Green 7); Dainippon Ink Chemicals's system

Fastogen GREEN SF (C.I. pigment Green 7); Dainippon Ink Chemicals's system

Phthalocyanine GREEN B308 (C.I. pigment Green 7); Adret pigment Co., Ltd. system

Phthalocyanine GREEN SAX (C.I. pigment Green 7); Adret pigment Co., Ltd. system

Cyanine GREEN 2G-550-D (C.I. pigment Green 7); Dainichiseika Color Chem's system

Cyanine GREEN 2GO (C.I. pigment Green 7); Dainichiseika Color Chem's system

Cyanine GREEN PBN-1 (C.I. pigment Green 7); Toyo Ink Manufacturing Co., Ltd.'s system

HELIOGEN BLUE L8605 (C.I. pigment Green 7); BASF AG's system

HELIOGEN BLUE K8730 (C.I. pigment Green 7); BASF AG's system

HELIOGEN BLUE D8725 (C.I. pigment Green 7); BASF AG's system

HELIOGEN BLUE L9361 (C.I. pigment green 36); BASF AG's system

Irgalite GREEN 6G (C.I. pigment green 36); Ciba Specialty Chemicals (below be designated as CSC) corporate system

HOSTAPERM GREEN 8G (C.I. pigment green 36); The Clariant corporate system

Fastogen GREEN 2KY (C.I. pigment green 36); The DIC corporate system

Lionol GREEN 2YS (C.I. pigment green 36); Toyo Ink Manufacturing Co., Ltd.'s system

Lionol GREEN 6YK (C.I. pigment green 36); Toyo Ink Manufacturing Co., Ltd.'s system

HOSTAPERM VIOLET RL-NF (C.I. pigment Violet 23); The Clariant corporate system

HOSTAPERM VIOLET RL02 (C.I. pigment Violet 23); The Clariant corporate system

HOSTAPERM VIOLET BL (C.I. pigment Violet 23); The Clariant corporate system

HOSTAPERM VIOLET P-RL (C.I. pigment Violet 23); The Clariant corporate system

HOSTAPERM VIOLET RLspec (C.I. pigment Violet 23); The Clariant corporate system

HOSTAPERM VIOLET RLspec-TS (C.I. pigment Violet 23); The Clariant corporate system

PV Fast Violet RL (C.I. pigment Violet 23); The Clariant corporate system

PV Fast Violet BLP (C.I. pigment Violet 23); The Clariant corporate system

Novotex Violet BL-PC VP 2429 (C.I. pigment Violet 23); The Clariant corporate system

Novotex Violet BL VP 2435 (C.I. pigment Violet 23); The Clariant corporate system

Fastogen Super Violet RN (C.I. pigment Violet 23); The DIC corporate system

Fastogen Super Violet RNS (C.I. pigment Violet 23); The DIC corporate system

Fastogen Super Violet RN-SU-02 (C.I. pigment Violet 23); The DIC corporate system

Fastogen Super Violet RVS (C.I. pigment Violet 23); The DIC corporate system

Fastogen Super Violet RXE (C.I. pigment Violet 23); The DIC corporate system

Fastogen Super Violet RXS (C.I. pigment Violet 23); The DIC corporate system

Lionogen Violet R6100 (C.I. pigment Violet 23); Toyo Ink Manufacturing Co., Ltd.'s system

Lionogen Violet R6200 (C.I. pigment Violet 23); Toyo Ink Manufacturing Co., Ltd.'s system

Oriengtal Fast Violet BL (C.I. pigment Violet 23); Toyo Ink Manufacturing Co., Ltd.'s system

Paliogen Violet L 5890 (C.I. pigment Violet 23); BASF AG's system

Crommophtal Violet GT (C.I. pigment Violet 23); The CSC corporate system

Crommophtal Violet B (C.I. pigment violet 3 7); The CSC corporate system

Novoperm Orange HL (C.I. pigment orange 36); The Clariant corporate system

Symuler Fast Orange 4183H (C.I. pigment orange 36); The DIC corporate system

Chromofine Orange 3700L (C.I. pigment orange 36); Dainichiseika Color Chem's system

Lionogen Orange R-F (C.I. pigment orange 36); Toyo Ink Manufacturing Co., Ltd.'s system

Novoperm Red HFG (C.I. pigment orange 38); The Clariant corporate system

Hostaperm Orange HGL (C.I. pigment orange 60); The Clariant corporate system

DisperBYK-168 (dispersion agent, BYK Chemie corporate system)

Solseperse 32000 (dispersion agent, Noveon corporate system)

FANCRYL 512A (being equivalent to exemplary compounds M-11, Hitachi Chemical Co., Ltd.'s system)

N-caprolactam (Aldrich corporate system)

Actilane 421 (ethoxylated neopentylglycol diacrylate, Acros corporate system)

NK ester AMP-10G (vinylformic acid phenoxy ethyl, Xin Zhong village chemical industry Co., Ltd. system)

Firstcure ST-1 (polymerization retarder, Chem First corporate system)

Lucirin TPO (light trigger, BASF AG's system)

Benzophenone (light trigger, Industrial Co., Ltd's system)

IRGACURE 184 (light trigger, CSC corporate system)

Byk 307 (tensio-active agent, BYK Chemie corporate system)

(sensitizing agent is also referred to as sensitizing agent to Firstcure ITX; Chem First corporate system)

(embodiment 1-1)

Synthesizing of＜polymerizable compound and polymkeric substance thereof 〉

-M1-1 synthetic-

Make 355.0 parts of 1,8-naphthalimides be dissolved in 1,500 part of N-Methyl pyrrolidone, add 0.57 part in oil of mirbane down at 25 ℃, to wherein dripping 301.4 parts of DBU (diazabicylo undecylene).Stir after 30 minutes, drip 412.1 parts of 1-chloro-4-methyl-benzenes, under 60 ℃, carried out heated and stirred again 4 hours.Add 2700 parts of Virahols, 900 parts of distilled water in this reaction solution, the limit is cooled to 5 ℃ of limits and stirs.The precipitate that obtains is leached, use washed with isopropyl alcohol, obtain 544.0 parts of polymerizable compound M1-1.

Can confirm to have obtained polymerizable compound M1-1 by the following NMR data that illustrate.

¹H-NMR(300MHz，CDCl ₃，δ)：8.61(d，2H)，8.21(d，2H)，7.75(t，2H)，7.25-7.60(m，4H)，6.66(m，1H)，5.73(dd，1H)，5.38(s，2H)，5.20(dd，1H)。

-M1-3 synthetic-

Make 19.7 parts of 1,8-naphthalimides be dissolved in 100 parts of N-Methyl pyrrolidone, add 11.1 parts of triethylamines and stirring.To wherein dripping 20.2 parts of 4-vinyl benzene SULPHURYL CHLORIDE, stirred 2 hours.Add 500 parts of distilled water in this reaction solution, the limit is cooled to 5 ℃ of limits and stirs.The precipitate that obtains is leached, use methanol wash, obtain 20.0 parts of polymerizable compound M1-3.

Can confirm to have obtained polymerizable compound M1-3 by the following NMR data that illustrate.

¹H-NMR(300MHz，CDCl ₃，δ)：8.61(d，2H)，8.21(d，2H)，8.01(d，2H)，7.75(t，2H)，7.60(d，2H)，6.76(m，1H)，5.93(dd，1H)，5.58(dd，1H)，5.40(d，2H)。

-graft copolymer 1-1 synthetic-

In the there-necked flask of nitrogen replacement, introduce 2.0 parts of above-mentioned M1-1, (AA-6: Toagosei Co., Ltd's system) 18.0 parts and methylethylketone are 20 parts to have the polymethylmethacrylate of methacryloyl endways; (new eastern science Co., Ltd.: Three-one Motor) stir, the limit feeds nitrogen limit heat temperature raising to 78 ℃ in flask with stirrer.To wherein adding 2,0.027 part of 2-azo two (2, the 4-methyl pentane nitrile) (the system V-65 of Wako Pure Chemical Industries, Ltd.) carried out heated and stirred 2 hours under 78 ℃.After 2 hours, add 0.027 part of V-65 again, heated and stirred 3 hours.The reaction solution that obtains under agitation is injected into 1; in 000 part of hexane; make the precipitation heat drying of generation, obtain graft copolymer 1-1 (above-mentioned illustration graft copolymer 1-1: monomer/terminal methyl group acryl polymethyl methacrylate copolymer of representing by M1-1).

It is 31,500 that the weight-average molecular weight (polystyrene conversion) of this graft copolymer 1-1 is used gpc measurement, result, confirms to have obtained polymkeric substance thus.

In addition, GPC uses Shodex GPC KF-804 (Showa Denko K. K's system) as pillar, uses THF as eluant, is that 0.8mL/min, column temperature are to measure under 40 ℃ at flow velocity, detects with RI.

-graft copolymer 1-2 synthetic-

In the there-necked flask of nitrogen replacement, introduce 2.0 parts of above-mentioned M1-1,3-(N; N-dimethylaminopropyl acrylamide) 2.0 parts, (AA-6: Toagosei Co., Ltd's system) 16.0 parts and methylethylketone are 20 parts to have the polymethylmethacrylate of methacryloyl endways; (new eastern science Co., Ltd.: Three-one Motor) stir, the limit feeds nitrogen limit heat temperature raising to 78 ℃ in flask with stirrer.To wherein adding 2,0.027 part of 2-azo two (2, the 4-methyl pentane nitrile) (the system V-65 of Wako Pure Chemical Industries, Ltd.) carried out heated and stirred 2 hours under 78 ℃.After 2 hours, add 0.027 part of V-65 again, heated and stirred 3 hours.The reaction solution that obtains under agitation is injected into 1; in 000 part of hexane; make the precipitation heat drying of generation; obtain graft copolymer 1-2 (above-mentioned illustration graft copolymer 1-8: monomer/3-(N, N-dimethylamino) propyl group acrylamide/terminal methyl group acryl polymethyl methacrylate copolymer of representing by M1-1).

It is 56,600 that the weight-average molecular weight (polystyrene conversion) of this graft copolymer 1-2 is used gpc measurement, result, confirms to have obtained polymkeric substance thus.

-graft copolymer 1-3 synthetic-

Except " polymethylmethacrylate that has methacryloyl endways " of the synthesis example of graft copolymer 1-1 being changed into " methoxy polyethylene glycol methacrylate-styrene polymer (the system NK ester M-230G of Xin Zhong village chemical industry Co., Ltd.) ", obtain graft copolymer 1-3 (above-mentioned illustration graft copolymer 1-2: monomer/polyoxyethylene glycol one (methyl) acrylate copolymer of representing by M1-1) in the same manner with the synthesis example of graft copolymer 1-1.

It is 24,500 that the weight-average molecular weight (polystyrene conversion) of this graft copolymer 1-3 is used gpc measurement, result, confirms to have obtained polymkeric substance thus.

-graft copolymer 1-4 synthetic-

Except " polymethylmethacrylate that has methacryloyl endways " of the synthesis example of graft copolymer 1-1 changed into " have endways methacryloyl butyl polyacrylate (AB-6: Toagosei Co., Ltd's system) ", obtain graft copolymer 1-4 (above-mentioned illustration graft copolymer 1-4: monomer/terminal methyl group acryl butyl polyacrylate multipolymer of representing by M1-1) in the same manner with the synthesis example of graft copolymer 1-1.

It is 28,800 that the weight-average molecular weight (polystyrene conversion) of this graft copolymer 1-4 is used gpc measurement, result, confirms to have obtained polymkeric substance thus.

-graft copolymer 1-5 synthetic-

Except the M1-1 with the synthesis example of graft copolymer 1-1 changes into M1-3, obtain graft copolymer 1-5 (above-mentioned illustration graft copolymer 5: monomer/terminal methyl group acryl polymethyl methacrylate copolymer of representing by M1-3) in the same manner with the synthesis example of graft copolymer 1-1.

It is 18,700 that the weight-average molecular weight (polystyrene conversion) of this graft copolymer 1-5 is used gpc measurement, result, confirms to have obtained polymkeric substance thus.

-graft copolymer 1-6 synthetic-

Except " 3-(N; N-dimethylaminopropyl acrylamide) " with the synthesis example of graft copolymer 1-2 changes into " methacrylic acid " in addition, obtain graft copolymer 1-6 (above-mentioned illustration graft copolymer 1-16: monomer/methacrylic acid/terminal methyl group acryl polymethyl methacrylate copolymer of representing by M1-1) in the same manner with the synthesis example of graft copolymer 1-2.

It is 19,800 that the weight-average molecular weight (polystyrene conversion) of this graft copolymer 1-6 is used gpc measurement, result, confirms to have obtained polymkeric substance thus.

(preparation of millbase A1-1)

300 parts of HEUCO GREEN 600703K

500 parts of Actilane421 (Akcros corporate system acrylate monomer)

200 parts of graft copolymer 1-1

Mentioned component is mixed, obtain pigment ink.In addition, the preparation of pigment grind base-material is by pigment ink being joined among the dispersion machine motor mill M50 (Eiger corporate system), and is that the zirconium oxide bead of 0.65mm disperses to carry out in 4 hours with the circumferential speed of 9m/s with diameter.

(preparation of millbase A1-2～A1-30)

Except pigment and graft copolymer being changed into pigment shown in the following table 1 and graft copolymer, prepare millbase A1-2～A1-30 in the same manner with millbase A1-1.

Table 1

Millbase	Pigment	Graft copolymer
			A1-2	HEUCO GREEN 600703K	1-2
A1-3	HEUCO GREEN 600703K	1-3
			A1-4	HEUCO GREEN 600703K	1-4
A1-5	Monastral GREEN GN-C	1-1
			A1-6	Monastral GREEN GNX-C	1-2
A1-7	Monastral GREEN GBX-C	1-3
			A1-8	HOSTAPERM GREEN GG01	1-1
A1-9	HOSTAPERM GREEN GNX-D	1-1
			A1-10	HOSTAPERM GREEN GNX-TS	1-2
A1-11	PV Fast GREEN GNX	1-3
			A1-12	Novotex GREEN GNX	1-5
A1-13	Fastogen GREEN S	1-3
			A1-14	Fastogen GREEN SF	1-4
A1-15	Phthalocyanine GREEN B308	1-5
			A1-16	Phthalocyanine GREEN SAX	1-2
A1-17	Cyanine GREEN 2G-550-D	1-1
			A1-18	Cyanine GREEN 2GO	1-2
A1-19	Cyanine GREEN PBN-1	1-4
			A1-20	HELIOGEN BLUE L8605	1-1
A1-21	HELIOGEN BLUE K8730	1-5
			A1-22	HELIOGEN BLUE D8725	1-1
A1-23	HELIOGEN BLUE L9361	1-6
			A1-24	Irgalite GREEN 6G	1-2
A1-25	HOSTAPERM GREEN 8G	1-6
			A1-26	Fastogen GREEN 2KY	1-1
A1-27	Lionol GREEN 2YS	1-2
			A1-28	Lionol GREEN 6YK	1-6
A1-29	HEUCO GREEN 600703K	DisperBYK-168
			A1-30	HEUCO GREEN 600703K	Solsperse32000

(preparation of millbase B1-1)

300 parts of HOSTAPERM VIOLET RL-NF

500 parts of Actilane421 (Akcros corporate system acrylate monomer)

200 parts of graft copolymer 1-1

Mentioned component is mixed, obtain pigment ink.In addition, the preparation of pigment grind base-material is by pigment ink being joined among the dispersion machine motor mill M50 (Eiger corporate system), and is that the zirconium oxide bead of 0.65mm disperses to carry out in 4 hours with the circumferential speed of 9m/s with diameter.

(preparation of millbase B1-2～B1-27)

Except pigment and graft copolymer being changed into pigment shown in the following table 2 and graft copolymer, prepare millbase B1-2～B1-27 in the same manner with millbase B1-1.

Table 2

Millbase	Pigment	Graft copolymer
			B1-2	HOSTAPERM VIOLET RL-NF	1-2
B1-3	HOSTAPERM VIOLET RL-NF	1-3
			B1-4	HOSTAPERM VIOLET RL-NF	1-4
B1-5	HOSTAPERM VIOLET RL02	1-1
			B1-6	HOSTAPERM VIOLET BL	1-2
B1-7	HOSTAPERM VIOLET P-RL	1-3
			B1-8	HOSTAPERM VIOLET RLspec	1-1
B1-9	HOSTAPERM VIOLET RLspec-TS	1-1
			B1-10	PVFast VioletRL	1-2
B1-11	PV Fast Violet BLP	1-3
			B1-12	Novotex Violet BL-PC VP 2429	1-5
B1-13	Novotex Violet BL VP 2435	1-3
			B1-14	Fastogen Super Violet RN	1-4
B1-15	Fastogen Super Violet RNS	1-6
			B1-16	Fastogen Super Violet RN-SU-02	1-2
B1-17	Fastogen Super Violet RVS	1-1
			B1-18	Fastogen Super Violet RXE	1-2
B1-19	Fastogen Super Violet RXS	1-4
			B1-20	Lionogen Violet R6100	1-1
B1-21	Lionogen Violet R6200	1-5
			B1-22	Oriengtal Fast Violet BL	1-1
B1-23	Paliogen Violet L 5890	1-1
			B1-24	Crommophtal Violet GT	1-2
B1-25	Crommophtal Violet B	1-6
			B1-26	HOSTAPERM VIOLET RL-NF	DisperBYK-168
B1-27	HOSTAPERM VIOLET RL-NF	Solsperse 32000

(preparation of millbase C1-1)

300 parts of Symuler Fast Orange 4183H

500 parts of Actilane421 (Akcros corporate system acrylate monomer)

200 parts of graft copolymer 1-1

Mentioned component is mixed, obtain pigment ink.In addition, the preparation of pigment grind base-material is by pigment ink being joined among the dispersion machine motor mill M50 (Eiger corporate system), and is that the zirconium oxide bead of 0.65mm disperses to carry out in 4 hours with the circumferential speed of 9m/s with diameter.

(preparation of millbase C1-2～C1-19)

Except pigment and graft copolymer being changed into pigment shown in the following table 3 and graft copolymer, prepare millbase C1-2～C1-19 in the same manner with millbase C1-1.

Table 3

Millbase	Pigment	Graft copolymer
			C1-2	Symuler Fast Orange 4183H	1-2
C1-3	Symuler Fast Orange 4183H	1-3
			C1-4	Symuler Fast Orange 4183H	1-4
C1-5	Symuler Fast Orange 4183H	1-5
			C1-6	Symuler Fast Orange 4183H	1-6
C1-7	Novoperm Orange HL	1-1
			C1-8	Novoperm Orange HL	1-2
C1-9	Novoperm Orange HL	1-3
			C1-10	Novoperm Orange HL	1-4
C1-11	Novoperm Orange HL	1-5
			C1-12	Novoperm Orange HL	1-6
C1-13	Chromofine Orange 3700L	1-1
			C1-14	LionogenOrange R-F	1-2
C1-15	Novoperm Red HFG	1-3
			C1-16	Novoperm Red HFG	1-4
C1-17	Novoperm Red HFG	1-5
			C1-18	Symuler Fast Orange 4183H	DisperBYK-168
C1-19	Symuler Fast Orange 4183H	Solsperse32000

(embodiment 1-1-1)

Following composition is stirred with the high speed water-cooling type agitator, obtain ink for inking.Viscosity is 17mPas.

(ink composite)

6.0 parts of millbase A1-1

35.4 parts of FANCRYL 512A

25.0 parts of N-caprolactams

20.0 parts of NK ester AMP-10G

0.05 part of Firstcure ST-1

8.5 parts of Lucirin TPO

3.0 parts of benzophenone

184 2.0 parts of IRGACURE

307 0.05 parts of BYK

0.1 part of dimethyl amino ethyl acrylate

(evaluation of printing ink)

The ink composite that use obtains carries out ink-vapor recording.

Solidified nature, storage stability, spray row property (spray row's reliability and spray nozzle clogging are restored continuously), flexibility and base material adhesivity are estimated.Evaluation result is shown in table 4.

＜storage stability 〉

The ink composite of embodiment and comparative example was kept for 4 weeks down at 60 ℃.

Metewand is as follows.

4: viscosity rises and is lower than 5%, and pigment particle size does not change

3: viscosity rises more than 5% and is lower than 10%, and pigment particle size does not change

2: viscosity rises more than 10% and is lower than 30%, and pigment particle size changes

1: viscosity rises more than 30%, and pigment particle size changes

" ink jet image recording method "

Use through the time before printing ink and at 60 ℃ of various ink composites that kept down for 4 weeks, and use ink-vapor recording experimental installation with piezo-electric type inkjet nozzle, carry out the record on printing medium.Ink supply system comprises main jar, supplying tubing, inking jar, strainer, piezo-electric type ink gun in front of ink gun, to partly carry out thermal insulation and heating from the inking jar to ink gun.Temperature sensor is separately positioned near the nozzle of inking jar and ink gun, and controlled temperature makes nozzle segment be always 45 ℃ ± 2 ℃.Drive the multiple size ink dot (multisize dot) that the piezo-electric type ink gun makes it possible to penetrate with the resolving power of 720 * 720dpi 8～30pl.Adjust exposure system, main-scanning speed and penetrate frequency, make that UV light is assembled after the inking and be 1630mW/cm ²Plane of exposure illumination, and the printing ink inking to printing medium begin after last 0.1 second the irradiation.In addition, making the accumulation light quantity that shines on the image is 4500mJ/cm ²UV-lamp is used the high mercury lamp (manufacturing of GS YuasaCorporation company) that solidifies of HAN250NL.In addition, said dpi represents counting of every 2.54cm among the present invention.In addition, use polyester film E5000 (thickness is that 125 μ m, Toyo Boseki K.K make) as printing medium.

The measuring method of＜curing sensitivity (solidified nature) 〉

Average the drawing of whole image that thickness is 12 μ m according to above-mentioned ink jet recording method, on the image surface after the uviolizing, by touching the viscosity degree of evaluation map picture, through the time before and after variation estimate according to following benchmark.

3: through the time before and after do not change.

2: through the time before and after a little a bit change, through the time after viscosity a little a bit change.

1: through the time before and after change bigger, through the time after do not solidify so that uncured ink transfer degree to hand.

＜flexible appraisal method: pliability test 〉

In the present embodiment, as the method for the flexibility of estimating the cured film of using the ink composite preparation that under 60 ℃, kept for 4 weeks, carried out pliability test.

According to above-mentioned ink jet image recording method, as printing medium, the average film thickness of drawing image portion is 12 μ m, 24 μ m, these three kinds of whole images of 36 μ m to use polyester film E5000 (thickness is that 125 μ m, Toyo Boseki K.K make).Pliability test is that the material bending under 25 ℃ condition that is recorded that will be formed with image once has flawless evaluation by definite image portion.In general, if the average film thickness thickening, the deformation that then produces in image portion when curved images portion increases, and is easy to generate crackle.That is, have the image portion thick by test and whether crack, can be used as the yardstick of flexibility than thick film.

Metewand is as described below.

4: average film thickness is that the sample of 12 μ m, 24 μ m, 36 μ m does not crack.

3: average film thickness is that the sample of 12 μ m, 24 μ m does not crack

2: average film thickness is that the sample of 12 μ m does not crack, and has produced crackle but average film thickness is the sample of 24 μ m on the curved part of image portion.

1: average film thickness is that all samples of 12 μ m, 24 μ m, 36 μ m has all produced crackle on the curved part of image portion.

＜material adhesion evaluation method: grid test (EN ISO2409) 〉

As printing medium, according to above-mentioned ink jet image recording method, the average film thickness of drawing image portion on each substrate is whole the image of 12 μ m to use PET (ester film E5000, thickness are 125 μ m, and Toyo Boseki K.K makes).Then, to various prints, carry out grid test (EN ISO2409).

Metewand is as described below.

1: have an appointment and 10% peel off

0: do not peel off

＜viscosity measurement 〉

Viscosimetric analysis in the present embodiment is to use Brookfield viscometer Brookfield LVDV-I (manufacturing of Brookfield company), and the rotor speed with 20rpm under 25 ℃ condition is carried out viscosimetric analysis.

＜spray row property 〉

Use above-mentioned ink-jet drawing apparatus, carry out following two kinds (A, B) and estimate.

[estimating A (spray row reliability continuously)]

Before the ink discharge device operation, utilize liquid of the present invention to repeat liquid circulation 15 minutes, and remove the remaining printing ink of printing ink contact part in device.Then, carry out 8 hours continuous use, calculate and produce the nozzle number of describing bad (not spraying row, distortion etc.).

4: spray takes place arrange bad

3:3 the following spray row of nozzle is bad

2:3 nozzle is above and be lower than 10 nozzles that spray row takes place is bad

1:10 the above generation spray of nozzle row is bad

In addition, all calculate with each shower nozzle.

[estimating B (spray nozzle clogging recovery)]

To estimating 10 bad shower nozzles of the spray row of generation more than the nozzle among the A, utilize liquid of the present invention to repeat liquid circulation 15 minutes, supply with printing ink once more, to describe, row's nozzle number is not sprayed in affirmation.

4: spray takes place arrange bad

3:3 the following generation spray of nozzle row is bad

2:3 nozzle is above and be lower than 10 nozzles that spray row takes place is bad

1:10 the above generation spray of nozzle row is bad

In addition, all calculate with each shower nozzle.

(embodiment 1-1-2～1-1-28 and comparative example 1-1-1 and 1-1-2)

Following composition is stirred with the high speed water-cooling type agitator, use the method identical, obtain ink for inking with embodiment 1-1-1.Viscosity is 17～22mPas.

In addition, carry out ink-vapor recording in the same manner, similarly estimate with embodiment 1-1-1.The results are shown in table 4.

Table 4

	The millbase of using	Solidified nature	Stability	Spray row property A	Spray row property B	Flexibility	Adhesivity
								Embodiment 1-1-1	A1-1	3	4	4	4	4	0
Embodiment 1-1-2	A1-2	3	4	4	4	4	0
								Embodiment 1-1-3	A1-3	3	4	4	4	4	0
Embodiment 1-1-4	A1-4	3	4	4	4	4	0
								Embodiment 1-1-5	A1-5	3	4	4	4	4	0
Embodiment 1-1-6	A1-6	3	4	4	4	4	0
								Embodiment 1-1-7	A1-7	3	4	4	4	4	0
Embodiment 1-1-8	A1-8	3	4	4	4	4	0
								Embodiment 1-1-9	A1-9	3	4	4	4	4	0
Embodiment 1-1-10	A1-10	3	4	4	4	4	0
								Embodiment 1-1-11	A1-11	3	4	4	4	4	0
Embodiment 1-1-12	A1-12	3	4	4	4	4	0
								Embodiment 1-1-13	A1-13	3	4	4	4	4	0
Embodiment 1-1-14	A1-14	3	4	4	4	4	0
								Embodiment 1-1-15	A1-15	3	4	4	4	4	0
Embodiment 1-1-16	A1-16	3	4	4	4	4	0
								Embodiment 1-1-17	A1-17	3	4	4	4	4	0
Embodiment 1-1-18	A1-18	3	4	4	4	4	0
								Embodiment 1-1-19	A1-19	3	4	4	4	4	0
Embodiment 1-1-20	A1-20	3	4	4	4	4	0
								Embodiment 1-1-21	A1-21	3	4	4	4	4	0
Embodiment 1-1-22	A1-22	3	4	4	4	4	0
								Embodiment 1-1-23	A1-23	3	4	4	4	4	0
Embodiment 1-1-24	A1-24	3	4	4	4	4	0
								Embodiment 1-1-25	A1-25	3	4	4	4	4	0
Embodiment 1-1-26	A1-26	3	4	4	4	4	0
								Embodiment 1-1-27	A1-27	3	4	4	4	4	0
Embodiment 1-1-28	A1-28	3	4	4	4	4	0
								Comparative example 1-1-1	A1-29	2	1	1	1	3	1
Comparative example 1-1-2	A1-30	2	1	2	2	3	1

(embodiment 1-2-1)

Except millbase A1-1 being changed into B1-1, obtain ink for inking in the same manner with embodiment 1-1-1.Viscosity is 18mPas.

In addition, carry out ink-vapor recording in the same manner, estimate with embodiment 1-1-1.The results are shown in table 5.

(embodiment 1-2-2～1-2-25 and comparative example 1-2-1 and 1-2-2)

Except millbase B1-1 being changed into the millbase shown in the table 5, obtain ink for inking in the same manner with embodiment 1-2-1.Viscosity is 17～22mPas.

Table 5

	The millbase of using	Solidified nature	Stability	Spray row property A	Spray row property B	Flexibility	Adhesivity
								Embodiment 1-2-1	B1-1	3	4	4	4	4	0
Embodiment 1-2-2	B1-2	3	4	4	4	4	0
								Embodiment 1-2-3	B1-3	3	4	4	4	4	0
Embodiment 1-2-4	B1-4	3	4	4	4	4	0
								Embodiment 1-2-5	B1-5	3	4	4	4	4	0
Embodiment 1-2-6	B1-6	3	4	4	4	4	0
								Embodiment 1-2-7	B1-7	3	4	4	4	4	0
Embodiment 1-2-8	B1-8	3	4	4	4	4	0
								Embodiment 1-2-9	B1-9	3	4	4	4	4	0
Embodiment 1-2-10	B1-10	3	4	4	4	4	0
								Embodiment 1-2-11	B1-11	3	4	4	4	4	0
Embodiment 1-2-12	B1-12	3	4	4	4	4	0
								Embodiment 1-2-13	B1-13	3	4	4	4	4	0
Embodiment 1-2-14	B1-14	3	4	4	4	4	0
								Embodiment 1-2-15	B1-15	3	4	4	4	4	0
Embodiment 1-2-16	B1-16	3	4	4	4	4	0
								Embodiment 1-2-17	B1-17	3	4	4	4	4	0
Embodiment 1-2-18	B1-18	3	4	4	4	4	0
								Embodiment 1-2-19	B1-19	3	4	4	4	4	0
Embodiment 1-2-20	B1-20	3	4	4	4	4	0
								Embodiment 1-2-21	B1-21	3	4	4	4	4	0
Embodiment 1-2-22	B1-22	3	4	4	4	4	0
								Embodiment 1-2-23	B1-23	3	4	4	4	4	0
Embodiment 1-2-24	B1-24	3	4	4	4	4	0
								Embodiment 1-2-25	B1-25	3	4	4	4	4	0
Comparative example 1-2-1	B1-26	2	1	1	1	3	1
								Comparative example 1-2-2	B1-27	2	1	2	2	3	1

(embodiment 1-3-1)

Except millbase A1-1 being changed into millbase C1-1, obtain ink for inking in the same manner with embodiment 1-1-1.Viscosity is 19mPas.

In addition, carry out ink-vapor recording in the same manner, estimate with embodiment 1-1-1.The results are shown in table 6.

(embodiment 1-3-2～1-3-25 and comparative example 1-3-1 and 1-3-2)

Except millbase C1-1 being changed into the millbase shown in the table 6, obtain ink for inking in the same manner with embodiment 1-3-1.Viscosity is 17～22mPas.

Table 6

	The millbase of using	Solidified nature	Stability	Spray row property A	Spray row property B	Flexibility	Adhesivity
								Embodiment 1-3-1	C1-1	3	4	4	4	4	0
Embodiment 1-3-2	C1-2	3	4	4	4	4	0
								Embodiment 1-3-3	C1-3	3	4	4	4	4	0
Embodiment 1-3-4	C1-4	3	4	4	4	4	0
								Embodiment 1-3-5	C1-5	3	4	4	4	4	0
Embodiment 1-3-6	C1-6	3	4	4	4	4	0
								Embodiment 1-3-7	C1-7	3	4	4	4	4	0
Embodiment 1-3-8	C1-8	3	4	4	4	4	0
								Embodiment 1-3-9	C1-9	3	4	4	4	4	0
Embodiment 1-3-10	C1-10	3	4	4	4	4	0
								Embodiment 1-3-11	C1-11	3	4	4	4	4	0
Embodiment 1-3-12	C1-12	3	4	4	4	4	0
								Embodiment 1-3-13	C1-13	3	4	4	4	4	0
Embodiment 1-3-14	C1-14	3	4	4	4	4	0
								Embodiment 1-3-15	C1-15	3	4	4	4	4	0
Embodiment 1-3-16	C1-16	3	4	4	4	4	0
								Embodiment 1-3-17	C1-17	3	4	4	4	4	0
Embodiment 1-3-18	C1-18	3	4	4	4	4	0
								Embodiment 1-3-19	C1-19	3	4	4	4	4	0
Embodiment 1-3-20	C1-20	3	4	4	4	4	0
								Embodiment 1-3-21	C1-21	3	4	4	4	4	0
Embodiment 1-3-22	C1-22	3	4	4	4	4	0
								Embodiment 1-3-23	C1-23	3	4	4	4	4	0
Embodiment 1-3-24	C1-24	3	4	4	4	4	0
								Embodiment 1-3-25	C1-25	3	4	4	4	4	0
Comparative example 1-3-1	C1-26	2	1	1	1	3	1
								Comparative example 1-3-2	C1-27	2	1	2	2	3	1

(embodiment 1-4)

Use is estimated the color reproduction of printed images by the characteristic printing ink that colored ink and embodiment 1-1-1, embodiment 1-2-1 and embodiment 1-3-1 obtain.

As colored ink, use cyan (Sericol corporate system EI), magenta (Sericol corporate system EI), yellow (Sericol corporate system EI), black (Sericol corporate system EI) printing ink.

Tone (a ^*, b ^*), brightness (L) measures with Gretag corporate system SPM100-II.

The solid line of Fig. 1 is the printed image data that is obtained by colored ink, and it is to use colored ink, on synthetic paper (prince tac Co., Ltd. system), uses above-mentioned drawing apparatus and the colour code data of complete 950 looks of equal distribution.Color reproduction (a of this expression colored ink ^*, b ^*) maximum region.

The dotted line of Fig. 1 represents to use the color reproduction (a of the printed images that the printing ink group obtains ^*, b ^*) maximum region, the characteristic printing ink that described printing ink group adds in above-mentioned colored ink by green, purple and the orange ink of embodiment 1-1-1, embodiment 1-2-1 and embodiment 1-3-1 preparation forms.

As a result, it is evident that, even present colored ink be difficult to the tone of color reproduction also can color reproduction.

(embodiment 2-1)

Synthesizing of＜polymerizable compound and polymkeric substance thereof 〉

-M2-1 synthetic-

Make the amino benzoglyoxaline of 2-be dissolved in 1,000 part of N-Methyl pyrrolidone for 133.2 parts, add 0.29 part in oil of mirbane down at 25 ℃.To wherein dripping 155.2 parts of 2-methacryloxyethyl isocyanic ester, stir after 30 minutes, stirred 1 hour down at 80 ℃, in this reaction solution, add 4,000 parts of methyl alcohol and stir.The precipitate that obtains is leached,, obtain 262.4 parts of polymerizable compound M2-1 with 1,200 part of washing of methyl alcohol.

Can confirm to have obtained polymerizable compound M2-1 by the following NMR data that illustrate.

¹H-NMR(300MHz，DMSO-d6，δ)：11.44(br，1H)，9.96(br，1H)，7.70(br，1H)，7.36(m，2H)，7.02(m，2H)，6.10(s，1H)，5.73(s，1H)，4.20(t，2H)，3.51(t，2H)，1.96(s，3H)。

-M2-2 synthetic-

Make 15.2 parts of 2-aminobenzothiazoles be dissolved in 100 parts of N-Methyl pyrrolidone, add 0.029 part in oil of mirbane down at 25 ℃.To wherein dripping 15.5 parts of 2-methacryloxyethyl isocyanic ester, stir after 30 minutes, stirred 1 hour down at 80 ℃, in this reaction solution, add 400 parts of methyl alcohol and stir.The precipitate that obtains is leached,, obtain 27.6 parts of polymerizable compound M2-2 with 100 parts of washings of methyl alcohol.

Can confirm to have obtained polymerizable compound M2-2 by the following NMR data that illustrate.

¹H-NMR(300MHz，DMSO-d6，δ)：11.43(br，1H)，7.72(br，1H)，7.34(m，2H)，7.01(m，2H)，6.10(s，1H)，5.73(s，1H)，4.20(t，2H)，3.51(t，2H)，1.96(s，3H)。

-graft copolymer 2-1 synthetic-

Except the M1-1 with the synthesis example of graft copolymer 1-1 changes into M2-1, obtain graft copolymer 2-1 (above-mentioned illustration graft copolymer 2-1: monomer/terminal methyl group acryl polymethyl methacrylate copolymer of representing by M2-1) in the same manner with the synthesis example of graft copolymer 1-1.

It is 19,900 that the weight-average molecular weight (polystyrene conversion) of this graft copolymer 2-1 is used gpc measurement, result, confirms to have obtained polymkeric substance thus.

-graft copolymer 2-2 synthetic-

Except the M1-1 with the synthesis example of graft copolymer 1-2 changes into M2-1; obtain graft copolymer 2-2 (above-mentioned illustration graft copolymer 2-8: monomer/3-(N, N-dimethylamino) propyl group acrylamide/terminal methyl group acryl polymethyl methacrylate copolymer of representing by M2-1) in the same manner with the synthesis example of graft copolymer 1-2.

It is 54,000 that the weight-average molecular weight (polystyrene conversion) of this graft copolymer 2-2 is used gpc measurement, result, confirms to have obtained polymkeric substance thus.

-graft copolymer 2-3 synthetic-

Except " polymethylmethacrylate that has methacryloyl endways " of the synthesis example of graft copolymer 2-1 being changed into " methoxy polyethylene glycol methacrylate-styrene polymer (the system NK ester M-230G of Xin Zhong village chemical industry Co., Ltd.) ", obtain graft copolymer 2-3 (above-mentioned illustration graft copolymer 2-2: monomer/polyoxyethylene glycol one (methyl) acrylate copolymer of representing by M2-1) in the same manner with the synthesis example of graft copolymer 2-1.

It is 26,700 that the weight-average molecular weight (polystyrene conversion) of this graft copolymer 2-3 is used gpc measurement, result, confirms to have obtained polymkeric substance thus.

-graft copolymer 2-4 synthetic-

Except the M2-1 with the synthesis example of graft copolymer 2-1 changes into M2-2, obtain graft copolymer 2-4 (above-mentioned illustration graft copolymer 2-5: monomer/terminal methyl group acryl polymethyl methacrylate copolymer of representing by M2-2) in the same manner with the synthesis example of graft copolymer 2-1.

It is 24,300 that the weight-average molecular weight (polystyrene conversion) of this graft copolymer 2-4 is used gpc measurement, result, confirms to have obtained polymkeric substance thus.

-graft copolymer 2-5 synthetic-

Except " 3-(N; N-dimethylaminopropyl acrylamide) " with the synthesis example of graft copolymer 2-2 changes into " methacrylic acid " in addition, obtain graft copolymer 2-5 (above-mentioned illustration graft copolymer 2-16: monomer/methacrylic acid/terminal methyl group acryl polymethyl methacrylate copolymer of representing by M2-1) in the same manner with the synthesis example of graft copolymer 2-2.

It is 19,400 that the weight-average molecular weight (polystyrene conversion) of this graft copolymer 2-5 is used gpc measurement, result, confirms to have obtained polymkeric substance thus.

(preparation of millbase A2-1)

300 parts of HEUCO GREEN 600703K

500 parts of Actilane421 (Akcros corporate system acrylate monomer)

200 parts of graft copolymer 2-1

Mentioned component is mixed, obtain pigment ink.In addition, the preparation of pigment grind base-material is by pigment ink being joined among the dispersion machine motor mill M50 (Eiger corporate system), and is that the zirconium oxide bead of 0.65mm disperses to carry out in 4 hours with the circumferential speed of 9m/s with diameter.

(preparation of millbase A2-2～A2-30)

Except pigment and graft copolymer being changed into pigment shown in the following table 7 and graft copolymer, prepare millbase A2-2～A2-30 in the same manner with millbase A2-1.

Table 7

Millbase	Pigment	Graft copolymer
			A2-2	HEUCO GREEN 600703K	2-2
A2-3	HEUCO GREEN 600703K	2-3
			A2-4	HEUCO GREEN 600703K	2-4
A2-5	Monastral GREEN GN-C	2-1
			A2-6	Monastral GREEN GNX-C	2-2
A2-7	Monastral GREEN GBX-C	2-3
			A2-8	HOSTAPERM GREEN GG01	2-1
A2-9	HOSTAPERM GREEN GNX-D	2-1
			A2-10	HOSTAPERM GREEN GNX-TS	2-2
A2-11	PV Fast GREEN GNX	2-3
			A2-12	Novotex GREEN GNX	2-5
A2-13	Fastogen GREEN S	2-3
			A2-14	Fastogen GREEN SF	2-4
A2-15	Phthalocyanine GREEN B308	2-5
			A2-16	Phthalocyanine GREEN SAX	2-2
A2-17	Cyanine GREEN 2G-550-D	2-1
			A2-18	Cyanine GREEN 2GO	2-2
A2-19	Cyanine GREEN PBN-1	2-4
			A2-20	HELIOGEN BLUE L8605	2-1
A2-21	HELIOGEN BLUE K8730	2-5
			A2-22	HELIOGEN BLUE D8725	2-1
A2-23	HELIOGEN BLUE L9361	2-4
			A2-24	Irgalite GREEN 6G	2-1
A2-25	HOSTAPERM GREEN 8G	2-5
			A2-26	Fastogen GREEN 2KY	2-1
A2-27	Lionol GREEN 2YS	2-2
			A2-28	Lionol GREEN 6YK	2-4
A2-29	HEUCO GREEN 600703K	DisperBYK-168
			A2-30	HEUCO GREEN 600703K	Solsperse32000

(preparation of millbase B2-1)

300 parts of HOSTAPERM VIOLET RL-NF

500 parts of Actilane421 (Akcros corporate system acrylate monomer)

200 parts of graft copolymer 2-1

Mentioned component is mixed, obtain pigment ink.In addition, the preparation of pigment grind base-material is by pigment ink being joined among the dispersion machine motor mill M50 (Eiger corporate system), and is that the zirconium oxide bead of 0.65mm disperses to carry out in 4 hours with the circumferential speed of 9m/s with diameter.

(preparation of millbase B2-2～B2-27)

Except pigment and graft copolymer being changed into pigment shown in the following table 8 and graft copolymer, prepare millbase B2-2～B2-27 in the same manner with millbase B2-1.

Table 8

Millbase	Pigment	Graft copolymer
			B2-2	HOSTAPERM VIOLET RL-NF	2-2
B2-3	HOSTAPERM VIOLET RL-NF	2-3
			B2-4	HOSTAPERM VIOLET RL-NF	2-4
B2-5	HOSTAPERM VIOLET RL02	2-1
			B2-6	HOSTAPERM VIOLET BL	2-2
B2-7	HOSTAPERM VIOLET P-RL	2-3
			B2-8	HOSTAPERM VIOLET RLspec	2-1
B2-9	HOSTAPERM VIOLET RLspec-TS	2-1
			B2-10	PV Fast Violet RL	2-2
B2-11	PV Fast Violet BLP	2-3
			B2-12	Novotex Violet BL-PC VP 2429	2-5
B2-13	Novotex Violet BL VP 2435	2-3
			B2-14	Fastogen Super Violet RN	2-4
B2-15	Fastogen Super Violet RNS	2-5
			B2-16	Fastogen Super Violet RN-SU-02	2-2
B2-17	Fastogen Super Violet RVS	2-1
			B2-18	Fastogen Super Violet RXE	2-2
B2-19	Fastogen Super Violet RXS	2-4
			B2-20	Lionogen Violet R6100	2-1
B2-21	Lionogen Violet R6200	2-5
			B2-22	Oriengtal Fast Violet BL	2-1
B2-23	Paliogen Violet L5890	2-1
			B2-24	Crommophtal Violet GT	2-2
B2-25	Crommophtal Violet B	2-4
			B2-26	HOSTAPERM VIOLET RL-NF	DisperBYK-168
B2-27	HOSTAPERMVIOLET RL-NF	Solsperse 32000

(preparation of millbase C2-1)

300 parts of Symuler Fast Orange 4183H

500 parts of Actilane421 (Akcros corporate system acrylate monomer)

200 parts of graft copolymer 2-1

Mentioned component is mixed, obtain pigment ink.In addition, the preparation of pigment grind base-material is by pigment ink being joined among the dispersion machine motor mill M50 (Eiger corporate system), and is that the zirconium oxide bead of 0.65mm disperses to carry out in 4 hours with the circumferential speed of 9m/s with diameter.

(preparation of millbase C2-2～C2-19)

Except pigment and graft copolymer being changed into pigment shown in the following table 9 and graft copolymer, prepare millbase C2-2～C2-19 in the same manner with millbase C2-1.

Table 9

Millbase	Pigment	Graft copolymer
			C2-2	Symuler Fast Orange 4183H	2-2
C2-3	Symuler Fast Orange 4183H	2-3
			C2-4	Symuler Fast Orange 4183H	2-4
C2-5	Symuler Fast Orange 4183H	2-5
			C2-6	Novoperm Orange HL	2-1
C2-7	Novoperm Orange HL	2-2
			C2-8	Novoperm Orange HL	2-3
C2-9	Novoperm Orange HL	2-4
			C2-10	Novoperm Orange HL	2-5
C2-11	Chromofine Orange 3700L	2-1
			C2-12	Chromofine Orange 3700L	2-2
C2-13	Chromofine Orange 3700L	2-3
			C2-14	LionogenOrange R-F	2-1
C2-15	Novoperm Red HFG	2-3
			C2-16	Novoperm Red HFG	2-4
C2-17	Novoperm Red HFG	2-5
			C2-18	Symuler Fast Orange 4183H	DisperBYK-168
C2-19	Symuler Fast Orange 4183H	Solsperse32000

(embodiment 2-1-1)

Except millbase A1-1 being changed into millbase A2-1, obtain ink for inking in the same manner with embodiment 1-1-1.

(evaluation of printing ink)

The ink composite that use obtains carries out ink-vapor recording.

Solidified nature, storage stability, spray row property (spray row's reliability and spray nozzle clogging are restored continuously), flexibility and base material adhesivity are estimated.Evaluation result is shown in table 10.

(embodiment 2-1-2～2-1-28 and comparative example 2-1-1 and 2-1-2)

Following composition is stirred with the high speed water-cooling type agitator, use the method identical, obtain ink for inking with embodiment 2-1-1.Viscosity is 17～22mPaS.

In addition, carry out ink-vapor recording in the same manner, similarly estimate with embodiment 2-1-1.The results are shown in table 10.

Table 10

	The millbase of using	Solidified nature	Stability	Spray row property A	Spray row property B	Flexibility	Adhesivity
								Embodiment 2-1-1	A2-1	3	4	4	4	4	0
Embodiment 2-1-2	A2-2	3	4	4	4	4	0
								Embodiment 2-1-3	A2-3	3	4	4	4	4	0
Embodiment 2-1-4	A2-4	3	4	4	4	4	0
								Embodiment 2-1-5	A2-5	3	4	4	4	4	0
Embodiment 2-1-6	A2-6	3	4	4	4	4	0
								Embodiment 2-1-7	A2-7	3	4	4	4	4	0
Embodiment 2-1-8	A2-8	3	4	4	4	4	0
								Embodiment 2-1-9	A2-9	3	4	4	4	4	0
Embodiment 2-1-10	A2-10	3	4	4	4	4	0
								Embodiment 2-1-11	A2-11	3	4	4	4	4	0
Embodiment 2-1-12	A2-12	3	4	4	4	4	0
								Embodiment 2-1-13	A2-13	3	4	4	4	4	0
Embodiment 2-1-14	A2-14	3	4	4	4	4	0
								Embodiment 2-1-15	A2-15	3	4	4	4	4	0
Embodiment 2-1-16	A2-16	3	4	4	4	4	0
								Embodiment 2-1-17	A2-17	3	4	4	4	4	0
Embodiment 2-1-18	A2-18	3	4	4	4	4	0
								Embodiment 2-1-19	A2-19	3	4	4	4	4	0
Embodiment 2-1-20	A2-20	3	4	4	4	4	0
								Embodiment 2-1-21	A2-21	3	4	4	4	4	0
Embodiment 2-1-22	A2-22	3	4	4	4	4	0
								Embodiment 2-1-23	A2-23	3	4	4	4	4	0
Embodiment 2-1-24	A2-24	3	4	4	4	4	0
								Embodiment 2-1-25	A2-25	3	4	4	4	4	0
Embodiment 2-1-26	A2-26	3	4	4	4	4	0
								Embodiment 2-1-27	A2-27	3	4	4	4	4	0
Embodiment 2-1-28	A2-28	3	4	4	4	4	0
								Comparative example 2-1-1	A2-29	2	1	1	1	3	1
Comparative example 2-1-2	A2-30	2	1	2	2	3	1

(embodiment 2-2-1)

Except millbase A2-1 being changed into millbase B2-1, obtain ink for inking in the same manner with embodiment 2-1-1.Viscosity is 18mPas.

In addition, carry out ink-vapor recording in the same manner, estimate with embodiment 2-1-1.The results are shown in table 11.

(embodiment 2-2-2～2-2-25 and comparative example 2-2-1 and 2-2-2)

Except millbase B2-1 being changed into the millbase shown in the table 11, obtain ink for inking in the same manner with embodiment 2-2-1.Viscosity is 17～22mPas.

Table 11

	The millbase of using	Solidified nature	Stability	Spray row property A	Spray row property B	Flexibility	Adhesivity
								Embodiment 2-2-1	B2-1	3	4	4	4	4	0
Embodiment 2-2-2	B2-2	3	4	4	4	4	0
								Embodiment 2-2-3	B2-3	3	4	4	4	4	0
Embodiment 2-2-4	B2-4	3	4	4	4	4	0
								Embodiment 2-2-5	B2-5	3	4	4	4	4	0
Embodiment 2-2-6	B2-6	3	4	4	4	4	0
								Embodiment 2-2-7	B2-7	3	4	4	4	4	0
Embodiment 2-2-8	B2-8	3	4	4	4	4	0
								Embodiment 2-2-9	B2-9	3	4	4	4	4	0
Embodiment 2-2-10	B2-10	3	4	4	4	4	0
								Embodiment 2-2-11	B2-11	3	4	4	4	4	0
Embodiment 2-2-12	B2-12	3	4	4	4	4	0
								Embodiment 2-2-13	B2-13	3	4	4	4	4	0
Embodiment 2-2-14	B2-14	3	4	4	4	4	0
								Embodiment 2-2-15	B2-15	3	4	4	4	4	0
Embodiment 2-2-16	B2-16	3	4	4	4	4	0
								Embodiment 2-2-17	B2-17	3	4	4	4	4	0
Embodiment 2-2-18	B2-18	3	4	4	4	4	0
								Embodiment 2-2-19	B2-19	3	4	4	4	4	0
Embodiment 2-2-20	B2-20	3	4	4	4	4	0
								Embodiment 2-2-21	B2-21	3	4	4	4	4	0
Embodiment 2-2-22	B2-22	3	4	4	4	4	0
								Embodiment 2-2-23	B2-23	3	4	4	4	4	0
Embodiment 2-2-24	B2-24	3	4	4	4	4	0
								Embodiment 2-2-25	B2-25	3	4	4	4	4	0
Comparative example 2-2-1	B2-26	2	1	1	1	3	1
								Comparative example 2-2-2	B2-27	2	1	2	2	3	1

(embodiment 2-3-1)

Except millbase A2-1 being changed into millbase C2-1, obtain ink for inking in the same manner with embodiment 2-1-1.Viscosity is 19mPaS.

In addition, carry out ink-vapor recording in the same manner, estimate with embodiment 2-1-1.The results are shown in table 12.

(embodiment 2-3-2～2-3-25 and comparative example 2-3-1 and 2-3-2)

Except millbase C2-1 being changed into the millbase shown in the table 12, obtain ink for inking in the same manner with embodiment 2-3-1.Viscosity is 17～22mPas.

Table 12

	The millbase of using	Solidified nature	Stability	Spray row property A	Spray row property B	Flexibility	Adhesivity
								Embodiment 2-3-1	C2-1	3	4	4	4	4	0
Embodiment 2-3-2	C2-2	3	4	4	4	4	0
								Embodiment 2-3-3	C2-3	3	4	4	4	4	0
Embodiment 2-3-4	C2-4	3	4	4	4	4	0
								Embodiment 2-3-5	C2-5	3	4	4	4	4	0
Embodiment 2-3-6	C2-6	3	4	4	4	4	0
								Embodiment 2-3-7	C2-7	3	4	4	4	4	0
Embodiment 2-3-8	C2-8	3	4	4	4	4	0
								Embodiment 2-3-9	C2-9	3	4	4	4	4	0
Embodiment 2-3-10	C2-10	3	4	4	4	4	0
								Embodiment 2-3-11	C2-11	3	4	4	4	4	0
Embodiment 2-3-12	C2-12	3	4	4	4	4	0
								Embodiment 2-3-13	C2-13	3	4	4	4	4	0
Embodiment 2-3-14	C2-14	3	4	4	4	4	0
								Embodiment 2-3-15	C2-15	3	4	4	4	4	0
Embodiment 2-3-16	C2-16	3	4	4	4	4	0
								Embodiment 2-3-17	C2-17	3	4	4	4	4	0
Embodiment 2-3-18	C2-18	3	4	4	4	4	0
								Embodiment 2-3-19	C2-19	3	4	4	4	4	0
Embodiment 2-3-20	C2-20	3	4	4	4	4	0
								Embodiment 2-3-21	C2-21	3	4	4	4	4	0
Embodiment 2-3-22	C2-22	3	4	4	4	4	0
								Embodiment 2-3-23	C2-23	3	4	4	4	4	0
Embodiment 2-3-24	C2-24	3	4	4	4	4	0
								Embodiment 2-3-25	C2-25	3	4	4	4	4	0
Comparative example 2-3-1	C2-26	2	1	1	1	3	1
								Comparative example 2-3-2	C2-27	2	1	2	2	3	1

(embodiment 2-4)

Use is estimated the color reproduction of printed images by the characteristic printing ink that colored ink and embodiment 2-1-1, embodiment 2-2-1 and embodiment 2-3-1 obtain.

As colored ink, use cyan (Sericol corporate system EI), magenta (Sericol corporate system EI), yellow (Sericol corporate system EI), black (Sericol corporate system EI) printing ink.

Tone (a ^*, b ^*), brightness (L) measures with Gretag corporate system SPM100-II.

The solid line of Fig. 2 is the printed image data that is obtained by colored ink, and it is to use colored ink, on synthetic paper (prince tac Co., Ltd. system), uses above-mentioned drawing apparatus and the colour code data of complete 950 looks of equal distribution.Color reproduction (a of this expression colored ink ^*, b ^*) maximum region.

The dotted line of Fig. 2 represents to use the color reproduction (a of the printed images that the printing ink group obtains ^*, b ^*) maximum region, the characteristic printing ink that described printing ink group adds in above-mentioned colored ink by green, purple and the orange ink of embodiment 2-1-1, embodiment 2-2-1 and embodiment 2-3-1 preparation forms.

As a result, it is evident that, even present colored ink be difficult to the tone of color reproduction also can color reproduction.

(embodiment 3-1)

Synthesizing of the chain-transfer agent of＜formula (3-3) expression and polymkeric substance 〉

As follows, synthetic T-1～T-13 (mercaptan compound of above-mentioned formula (3-3) expression).

[synthesis example T-1]

Make Dipentaerythritol six (3-mercaptopropionic acid ester) (DPMP; Sakai Chemical Industry Co., Ltd.'s system) 7.83 parts and the compound (A-1) that has following pigment adsorption structure and have a carbon-to-carbon double bond are dissolved in 93.60 parts of dimethyl formamides for 15.57 parts, under nitrogen gas stream, are heated to 70 ℃.To wherein adding 2,0.06 part of 2 '-azo two (2, the 4-methyl pentane nitrile) (V-65, Wako Pure Chemical Industries, Ltd.'s system) also heated 3 hours.Add 0.06 part of V-65 again, under nitrogen gas stream, reacted 3 hours down at 70 ℃.By being cooled to room temperature, obtain 20% solution of mercaptan compound as follows (chain-transfer agent T-1).

T-1 (1/5 adds adult)

[synthesis example T-2]

15.57 parts of the compounds (A-1), the dimethyl formamide that have above-mentioned pigment adsorption structure and have a carbon-to-carbon double bond in making above-mentioned synthesis example T-1 changed into for 93.60 parts 89.78 parts of 14.61 parts of the compounds (A-2), the dimethyl formamides that have following pigment adsorption structure and have carbon-to-carbon double bond, obtains 20% solution of mercaptan compound as follows (chain-transfer agent T-2) in the same manner with above-mentioned synthesis example T-1.

T-2 (1/5 adds adult)

[synthesis example T-3]

15.57 parts of the compounds (A-1), the dimethyl formamide that have above-mentioned pigment adsorption structure and have a carbon-to-carbon double bond in making above-mentioned synthesis example T-1 changed into for 93.60 parts 101.4 parts of 17.52 parts of the compounds (A-3), the dimethyl formamides that have following pigment adsorption structure and have carbon-to-carbon double bond, obtains 20% solution of mercaptan compound as follows (chain-transfer agent T-3) in the same manner with above-mentioned synthesis example T-1.

T-3 (1/5 adds adult)

[synthesis example T-4]

Make tetramethylolmethane four (3-mercaptopropionic acid ester) (PEMP; Sakai Chemical Industry Co., Ltd.'s system) 4.89 parts and the compound (A-4) that has following pigment adsorption structure and have a carbon-to-carbon double bond are dissolved in 77.20 parts of dimethyl formamides for 14.41 parts, under nitrogen gas stream, are heated to 70 ℃.To wherein adding 2,0.04 part of 2 '-azo two (2, the 4-methyl pentane nitrile) (V-65, Wako Pure Chemical Industries, Ltd.'s system) also heated 3 hours.Add 0.04 part of V-65 again, under nitrogen gas stream, reacted 3 hours down at 70 ℃.By being cooled to room temperature, obtain 20% solution of mercaptan compound as follows (chain-transfer agent T-4).

[synthesis example T-5]

15.57 parts of the compounds (A-1), the dimethyl formamide that have above-mentioned pigment adsorption structure and have a carbon-to-carbon double bond in making above-mentioned synthesis example T-1 changed into for 93.60 parts 30.54 parts of 5.26 parts of the compounds (A-5) having following pigment adsorption structure and have carbon-to-carbon double bond, 1-methoxyl group-2-propyl alcohol, obtains 30% solution of mercaptan compound as follows (chain-transfer agent T-5) in the same manner with above-mentioned synthesis example T-1.

[synthesis example T-6]

15.57 parts of the compounds (A-1), the dimethyl formamide that have above-mentioned pigment adsorption structure and have a carbon-to-carbon double bond in making above-mentioned synthesis example T-1 changed into for 93.60 parts 29.25 parts of 4.71 parts of the compounds (A-6) having following pigment adsorption structure and have carbon-to-carbon double bond, 1-methoxyl group-2-propyl alcohol, obtains 30% solution of mercaptan compound as follows (chain-transfer agent T-6) in the same manner with above-mentioned synthesis example T-1.

T-6 (1/5 adds adult)

[synthesis example T-7]

Make Dipentaerythritol six (3-mercaptopropionic acid ester) (DPMP; Sakai Chemical Industry Co., Ltd.'s system) 7.83 parts and 6.51 parts of compounds (A-7) having following pigment adsorption structure and have a carbon-to-carbon double bond are dissolved in 33.45 parts of 1-methoxyl groups-2-propyl alcohol, under nitrogen gas stream, are heated to 70 ℃.To wherein adding 2,0.06 part of 2 '-azo two (2, the 4-methyl pentane nitrile) (V-65, Wako Pure Chemical Industries, Ltd.'s system) also heated 3 hours.Add 0.06 part of V-65 again, under nitrogen gas stream, reacted 3 hours down at 70 ℃.By being cooled to room temperature, obtain 30% solution of mercaptan compound as follows (chain-transfer agent T-7).

[synthesis example T-8]

6.51 parts of the compounds (A-7), the 1-methoxyl group-2-propyl alcohol that have above-mentioned pigment adsorption structure and have a carbon-to-carbon double bond in making above-mentioned synthesis example T-7 changed into for 33.45 parts 31.81 parts of 5.80 parts of the compounds (A-8) having following pigment adsorption structure and have carbon-to-carbon double bond, 1-methoxyl group-2-propyl alcohol, obtains 30% solution of mercaptan compound as follows (chain-transfer agent T-8) in the same manner with above-mentioned synthesis example T-7.

[synthesis example T-9]

6.51 parts of the compounds (A-7), the 1-methoxyl group-2-propyl alcohol that have above-mentioned pigment adsorption structure and have a carbon-to-carbon double bond in making above-mentioned synthesis example T-7 changed into for 33.45 parts 47.35 parts of 12.46 parts of the compounds (A-9), the dimethyl formamides that have following pigment adsorption structure and have carbon-to-carbon double bond, obtains 30% solution of mercaptan compound as follows (chain-transfer agent T-9) in the same manner with above-mentioned synthesis example T-7.

T-9 (1/5 adds adult)

[synthesis example T-10]

6.51 parts of the compounds (A-7), the 1-methoxyl group-2-propyl alcohol that have above-mentioned pigment adsorption structure and have a carbon-to-carbon double bond in making above-mentioned synthesis example T-7 changed into for 33.45 parts 42.67 parts of 10.46 parts of the compounds (A-10), the dimethyl formamides that have following pigment adsorption structure and have carbon-to-carbon double bond, obtains 30% solution of mercaptan compound as follows (chain-transfer agent T-10) in the same manner with above-mentioned synthesis example T-7.

T-10 (1/5 adds adult)

[synthesis example T-11]

6.51 parts of the compounds (A-7), the 1-methoxyl group-2-propyl alcohol that have above-mentioned pigment adsorption structure and have a carbon-to-carbon double bond in making above-mentioned synthesis example T-7 changed into for 33.45 parts 36.61 parts of 7.86 parts of the compounds (A-11) having following pigment adsorption structure and have carbon-to-carbon double bond, 1-methoxyl group-2-propyl alcohol, obtains 30% solution of mercaptan compound as follows (chain-transfer agent T-11) in the same manner with above-mentioned synthesis example T-7.

T-11 (1/5 adds adult)

[synthesis example T-12]

Make tetramethylolmethane four (3-mercaptopropionic acid ester) (PEMP; Sakai Chemical Industry Co., Ltd.'s system) 4.89 parts and 3.90 parts of compounds (A-12) having following pigment adsorption structure and have a carbon-to-carbon double bond are dissolved in 20.51 parts of 1-methoxyl groups-2-propyl alcohol, under nitrogen gas stream, are heated to 70 ℃.To wherein adding 2,0.04 part of 2 '-azo two (2, the 4-methyl pentane nitrile) (V-65, Wako Pure Chemical Industries, Ltd.'s system) also heated 3 hours.Add 0.04 part of V-65 again, under nitrogen gas stream, reacted 3 hours down at 70 ℃.By being cooled to room temperature, obtain 30% solution of mercaptan compound as follows (chain-transfer agent T-12).

[synthesis example T-13]

Make Dipentaerythritol six (3-mercaptopropionic acid ester) (DPMP; Sakai Chemical Industry Co., Ltd.'s system) 7.83 parts and 4.55 parts of compounds (A-13) having following pigment adsorption structure and have a carbon-to-carbon double bond are dissolved in 28.90 parts of 1-methoxyl groups-2-propyl alcohol, under nitrogen gas stream, are heated to 70 ℃.To wherein adding 2,0.04 part of 2 '-azo two (2, the 4-methyl pentane nitrile) (V-65, Wako Pure Chemical Industries, Ltd.'s system) also heated 3 hours.Add 0.04 part of V-65 again, under nitrogen gas stream, reacted 3 hours down at 70 ℃.By being cooled to room temperature, obtain 30% solution of mercaptan compound as follows (chain-transfer agent T-13).

[synthesis example T-14]

6.51 parts of the compounds (A-7), the 1-methoxyl group-2-propyl alcohol that have above-mentioned pigment adsorption structure and have a carbon-to-carbon double bond in making above-mentioned synthesis example T-7 changed into for 33.45 parts 44.05 parts of 11.05 parts of the compounds (A-14), the dimethyl formamides that have following pigment adsorption structure and have carbon-to-carbon double bond, obtains 30% solution of mercaptan compound as follows (chain-transfer agent T-14) in the same manner with above-mentioned synthesis example T-7.

＜polymer P-1～P-28's is synthetic 〉

Below, synthetic above-mentioned C composition of the present invention (P-1～P-28).

[synthesis example P-1]

46.80 parts of 20% solution and the methyl methacrylate (MMA of the chain-transfer agent T-1 that will obtain by above-mentioned synthesis example T-1; Monomer) 20 parts mixing solutions is heated to 80 ℃ under nitrogen gas stream.To wherein adding 2,0.013 part of 2 '-azo two (isopropyl cyanide) (AIBN, Wako Pure Chemical Industries, Ltd.'s system) and heat 3 hours after, add 0.013 part of AIBN once more, under nitrogen gas stream, 80 ℃ of reactions 3 hours down.Then, be cooled to room temperature, use acetone diluted.After using a large amount of methyl alcohol to make its redeposition, carry out vacuum-drying, thereby obtain 19 parts of following polymkeric substance (P-1: the weight-average molecular weight through polystyrene conversion is 14,000) solids.

[synthesis example P-2]

Except being changed into 23.40 parts, AIBN by 46.80 parts, 20% solution of the chain-transfer agent T-1 among the above-mentioned synthesis example P-1 changes into 0.007 part by 0.013 part, obtain 23 parts of following polymkeric substance (P-2: the weight-average molecular weight through polystyrene conversion is 30,000) solids in the same manner with above-mentioned synthesis example P-1.

[synthesis example P-3]

Except 20 parts of the methyl methacrylates among the above-mentioned synthesis example P-1 being changed into 8.5 parts of 19.5 parts of butyl methacrylate and 2-hydroxyethyl methacrylates, obtain 20 parts of following polymkeric substance (P-3: the weight-average molecular weight through polystyrene conversion is 15,000) solids in the same manner with above-mentioned synthesis example P-1.

[synthesis example P-4～P-12]

Except the amount of the chain-transfer agent among the synthesis example P-1, monomeric kind and amount, AIBN and redeposition method are changed, obtain following polymkeric substance (P-4～P-12) in the same manner with above-mentioned synthesis example P-1 as following table 13.

Table 13

Synthesis example	Chain-transfer agent	Monomer	AIBN	The redeposition method	Weight-average molecular weight	The output of macromolecular compound
							P-4	44.89 part T-2 solution	MMA20 part	0.013 part	Use the methyl alcohol redeposition	15,000	24 parts
P-5	22.45 part T-2 solution	MMA20 part	0.007 part	Use the methyl alcohol redeposition	30,000	22 parts
							P-6	50.70 part T-3 solution	BMA19.5 part HEMA8.5 part	0.013 part	Use the methyl alcohol redeposition	14,000	25 parts
P-7	25.35 part T-3 solution	BMA19.5 part HEMA8.5 part	0.007 part	Use the methyl alcohol redeposition	28,000	22 parts
							P-8	12.87 part T-4 solution	BMA19.5 part HEMA8.5 part	0.007 part	Use the methyl alcohol redeposition	29,000	20 parts
P-9	17.45 part T-5 solution	BMA19.5 part HEMA8.5 part	0.013 part	Use the methyl alcohol redeposition	14,000	17 parts
							P-10	8.73 part T-5 solution	MMA20 part	0.007 part	Use the methyl alcohol redeposition	24,000	15 parts
P-11	16.71 part T-6 solution	MMA20 part	0.013 part	Use the methyl alcohol redeposition	15,000	17 parts
							P-12	8.36 part T-6 solution	MMA20 part	0.007 part	Use the methyl alcohol redeposition	31,000	18 parts

The MMA methyl methacrylate

The BMA n-BMA

HEMA methacrylic acid 2-hydroxyl ethyl ester

Below show the structure of synthetic polymkeric substance.In addition, (P-4) etc. sign is the sequence number of the synthesis example in the above-mentioned table 13 of expression.

[synthesis example P-13]

To under nitrogen gas stream, be heated to 80 ℃ by the mixing solutions of 20 parts of 19.11 parts of 30% solution of the chain-transfer agent T-7 described in the above-mentioned synthesis example T-7 and methyl methacrylates.To wherein adding 2,0.013 part of 2 '-azo two (isopropyl cyanide) (AIBN, Wako Pure Chemical Industries, Ltd.'s system) and heat 3 hours after, add 0.013 part of AIBN once more, under nitrogen gas stream, 80 ℃ of reactions 3 hours down.Then, be cooled to room temperature, use acetone diluted.After using a large amount of methyl alcohol to make its redeposition, carry out vacuum-drying, thereby obtain 13 parts of following polymkeric substance as follows (P-13: the weight-average molecular weight through polystyrene conversion is 12,000) solids.

[synthesis example P-14]

Change into 0.007 part by 0.013 part except changing into 9.56 parts, AIBN by 19.11 parts at 30% solution of the chain-transfer agent T-7 among the synthesis example P-13, obtain 14 parts of following polymkeric substance as follows (P-14: the weight-average molecular weight through polystyrene conversion is 20,000) solids in the same manner with above-mentioned synthesis example P-13.

[synthesis example P-15]

Except will be 20 parts of the methyl methacrylates among the above-mentioned synthesis example P-13 be changed into 8.5 parts of 19.5 parts of butyl methacrylate and 2-hydroxyethyl methacrylates, obtain 13 parts of following polymkeric substance (P-15: the weight-average molecular weight through polystyrene conversion is 13,000) solids in the same manner with above-mentioned synthesis example P-13.

[synthesis example P-16～P-27]

Except will be the amount of the chain-transfer agent among the above-mentioned synthesis example P-1, monomeric kind and amount, AIBN and redeposition method change, obtain polymkeric substance (P-16～P-27) in the same manner with above-mentioned synthesis example P-13 as following table 14.

Table 14

Synthesis example	Chain-transfer agent	Monomer	AIBN	The redeposition method	Weight-average molecular weight	The output of macromolecular compound
							P-16	9.56 part T-7 solution	MMA19 part MAA1 part	0.007 part	With methanol (1/1) redeposition	23,000	15 parts
P-17	9.03 part T-7 solution	MMA18 part NK ester SA2 part	0.007 part	With methanol (1/1) redeposition	23,000	16 parts
							P-18	18.18 part T-8 solution	MMA20 part	0.013 part	Use the methyl alcohol redeposition	13,000	11 parts
P-19	9.09 part T-8 solution	MMA20 part	0.007 part	Use the methyl alcohol redeposition	23,000	12 parts
							P-20	18.18 part T-8 solution	BMA19.5 part HEMA8.5 part	0.013 part	Use the methyl alcohol redeposition	16,000	11 parts
P-21	13.53 part T-9 solution	MMA20 part	0.007 part	Use the methyl alcohol redeposition	27,000	13 parts
							P-22	12.19 part T-10 solution	MMA20 part	0.007 part	Use the methyl alcohol redeposition	26,000	11 parts
P-23	12.13 part T-14 solution	MMA20 part	0.007 part	Use the methyl alcohol redeposition	28,000	10 parts
							P-24	20.92 part T-11 solution	MMA20 part	0.013 part	Use the methyl alcohol redeposition	15,000	18 parts
P-25	10.46 part T-11 solution	MMA20 part	0.007 part	Use the methyl alcohol redeposition	32,000	19 parts
							P-26	20.92 part T-11 solution	BMA19.5 part HEMA8.5 part	0.013 part	Use the methyl alcohol redeposition	17,000	22 parts
P-27	11.72 part T-12 solution	MMA20 part	0.013 part	Use the methyl alcohol redeposition	11,000	11 parts

The MMA methyl methacrylate

The MAA methacrylic acid

The BMA n-BMA

HEMA methacrylic acid 2-hydroxyl ethyl ester

NK ester SA (Xin Zhong village chemical industry Co., Ltd. system): 2-methacryloyloxyethyl.uccinate

Below show the structure of synthetic polymkeric substance.In addition, (P-16) etc. sign is the sequence number of the synthesis example in the above-mentioned table 14 of expression.

[synthesis example P-28]

To under nitrogen gas stream, be heated to 90 ℃ by the mixing solutions of 4.66 parts of 4.99 parts of 30% solution of the chain-transfer agent T-13 described in the above-mentioned synthesis example T-13 and 20.0 parts of methyl methacrylates, 1-methoxyl groups-2-propyl alcohol.The limit was stirred this mixed solution limit and dripped 2 in 2.5 hour, the mixing solutions that 0.139 part of 2 '-azo-bis-iso-dimethyl (V-601, Wako Pure Chemical Industries, Ltd.'s system), 1-methoxyl group-5.36 parts of 2-propyl alcohol, acetic acid (1-methoxyl group-2-third) ester are 9.40 parts.After drip finishing,, drop into the mixing solutions of 4.00 parts of 0.046 part of 2,2 '-azo-bis-iso-dimethyls, 1-methoxyl group-2-propyl group acetic ester then, reacted again 2 hours 90 ℃ of reactions 2.5 hours down.In this reaction solution, add 1-methoxyl group-1.52 parts of 2-propyl alcohol, 21.7 parts of acetic acid (1-methoxyl group-2-third) esters, be cooled to room temperature.After using a large amount of methyl alcohol to make its redeposition, carry out vacuum-drying, thereby obtain the solid of polymkeric substance as follows (P-28: the weight-average molecular weight through polystyrene conversion is 25,000).

(preparation of millbase A3-1)

300 parts of HEUCO GREEN 600703K

500 parts of Actilane421 (Akcros corporate system acrylate monomer)

Polymkeric substance-1 200 part

Mentioned component is mixed, obtain pigment ink.In addition, the preparation of pigment grind base-material is by pigment ink being joined among the dispersion machine motor mill M50 (Eiger corporate system), and is that the zirconium oxide bead of 0.65mm disperses to carry out in 4 hours with the circumferential speed of 9m/s with diameter.

(preparation of millbase A3-2～A3-30)

Except being pigment shown in the following table 15 and the polymkeric substance with pigment and polymers to alter, prepare millbase A3-2～A3-30 in the same manner with millbase A3-1.

Table 15

Millbase	Pigment	Polymkeric substance
			A3-2	HEUCO GREEN 600703K	P-2
A3-3	HEUCO GREEN 600703K	P-3
			A3-4	HEUCO GREEN 600703K	P-4
A3-5	Monastral GREEN GN-C	P-5
			A3-6	Monastral GREEN GNX-C	P-6
A3-7	Monastral GREEN GBX-C	P-7
			A3-8	HOSTAPERM GREEN GG01	P-8
A3-9	HOSTAPERM GREEN GNX-D	P-9
			A3-10	HOSTAPERM GREEN GNX-TS	P-10
A3-11	PV Fast GREEN GNX	P-11
			A3-12	Novotex GREEN GNX	P-12
A3-13	Fastogen GREEN S	P-13
			A3-14	Fastogen GREEN SF	P-14
A3-15	Phthalocyanine GREEN B308	P-15
			A3-16	Phthalocyanine GREEN SAX	P-16
A3-17	Cyanine GREEN 2G-550-D	P-17
			A3-18	Cyanine GREEN 2GO	P-18
A3-19	Cyanine GREEN PBN-1	P-19
			A3-20	HELIOGEN BLUE L8605	P-20
A3-21	HELIOGEN BLUE K8730	P-21
			A3-22	HELIOGEN BLUE D8725	P-22
A3-23	HELIOGEN BLUE L9361	P-23
			A3-24	Irgalite GREEN 6G	P-24
A3-25	HOSTAPERM GREEN 8G	P-25
			A3-26	Fastogen GREEN 2KY	P-26
A3-27	Lionol GREEN 2YS	P-27
			A3-28	Lionol GREEN 6YK	P-28
A3-29	HEUCO GREEN 600703K	DisperBYK-168
			A3-30	HEUCO GREEN 600703K	Solsperse32000

(preparation of millbase B3-1)

300 parts of HOSTAPERM VIOLET RL-NF

500 parts of Actilane421 (Akcros corporate system acrylate monomer)

Polymer P-1 200 part

Mentioned component is mixed, obtain pigment ink.In addition, the preparation of pigment grind base-material is by pigment ink being joined among the dispersion machine motor mill M50 (Eiger corporate system), and is that the zirconium oxide bead of 0.65mm disperses to carry out in 4 hours with the circumferential speed of 9m/s with diameter.

(preparation of millbase B3-2～B3-27)

Except being pigment shown in the following table 16 and the polymkeric substance with pigment and polymers to alter, prepare millbase B3-2～B3-27 in the same manner with millbase B3-1.

Table 16

Millbase	Pigment	Polymkeric substance
			B3-2	HOSTAPERM VIOLET RL-NF	P-2
B3-3	HOSTAPERM VIOLET RL-NF	P-4
			B3-4	HOSTAPERM VIOLET RL-NF	P-5
B3-5	HOSTAPERM VIOLET RL02	P-1
			B3-6	HOSTAPERM VIOLET BL	P-2
B3-7	HOSTAPERM VIOLET P-RL	P-4
			B3-8	HOSTAPERM VIOLET RLspec	P-5
B3-9	HOSTAPERM VIOLET RLspec-TS	P-6
			B3-10	PV Fast Violet RL	P-7
B3-11	PV Fast Violet BLP	P-10
			B3-12	Novotex Violet BL-PC VP 2429	P-11
B3-13	Novotex Violet BL VP 2435	P-12
			B3-14	Fastogen Super Violet RN	P-13
B3-15	Fastogen Super Violet RNS	P-14
			B3-16	Fastogen Super Violet RN-SU-02	P-15
B3-17	Fastogen Super Violet RVS	P-18
			B3-18	Fastogen Super Violet RXE	P-19
B3-19	Fastogen Super Violet RXS	P-20
			B3-20	Lionogen Violet R6100	P-21
B3-21	Lionogen Violet R6200	P-24
			B3-22	Oriengtal Fast Violet BL	P-25
B3-23	Paliogen Violet L5890	P-26
			B3-24	Crommophtal Violet GT	P-27
B3-25	Crommophtal Violet B	P-28
			B3-26	HOSTAPERM VIOLET RL-NF	DisperBYK-168
B3-27	HOSTAPERM VIOLET RL-NF	Solsperse32000

(preparation of millbase C3-1)

300 parts of Symuler Fast Orange 4183H

500 parts of Actilane421 (Akcros corporate system acrylate monomer)

Polymer P-1 200 part

Mentioned component is mixed, obtain pigment ink.In addition, the preparation of pigment grind base-material is by pigment ink being joined among the dispersion machine motor mill M50 (Eiger corporate system), and is that the zirconium oxide bead of 0.65mm disperses to carry out in 4 hours with the circumferential speed of 9m/s with diameter.

(preparation of millbase C3-2～C3-19)

Except being pigment shown in the following table 9 and the polymkeric substance with pigment and polymers to alter, prepare millbase C3-2～C3-19 in the same manner with millbase C3-1.

Table 17

Millbase	Pigment	Polymkeric substance
			C3-2	Symuler Fast Orange 4183H	P-2
C3-3	Symuler Fast Orange 4183H	P-4
			C3-4	Symuler Fast Orange 4183H	P-5
C3-5	Symuler Fast Orange 4183H	P-6
			C3-6	Symuler Fast Orange 4183H	P-7
C3-7	Novoperm Orange HL	P-1
			C3-8	Novoperm Orange HL	P-11
C3-9	Novoperm Orange HL	P-12
			C3-10	Novoperm Orange HL	P-13
C3-11	Novoperm Orange HL	P-14
			C3-12	Novoperm Orange HL	P-15
C3-13	Chromofine Orange 3700L	P-18
			C3-14	LionogenOrange R-F	P-19
C3-15	Novoperm Red HFG	P-20
			C3-16	Novoperm Red HFG	P-21
C3-17	Novoperm Red HFG	P-28
			C3-18	Symuler Fast Orange 4183H	DisperBYK-168
C3-19	Symuler Fast Orange 4183H	Solsperse32000

(embodiment 3-1-1)

Except millbase A1-1 being changed into millbase A3-1, obtain ink for inking in the same manner with embodiment 1-1-1.Viscosity is 17mPas.

(embodiment 3-1-2～3-1-28 and comparative example 3-1-1 and 3-1-2)

Except millbase A3-1 being changed into the millbase shown in the table 18, use the method identical with embodiment 3-1-1, obtain ink for inking.Viscosity is 17～22mPas.

In addition, carry out ink-vapor recording in the same manner, similarly estimate with embodiment 3-1-1.The results are shown in table 18.

Table 18

	The millbase of using	Solidified nature	Stability	Spray row property A	Spray row property B	Flexibility	Adhesivity
								Embodiment 3-1-1	A3-1	3	4	4	4	4	0
Embodiment 3-1-2	A3-2	3	4	4	4	4	0
								Embodiment 3-1-3	A3-3	3	4	4	4	4	0
Embodiment 3-1-4	A3-4	3	4	4	4	4	0
								Embodiment 3-1-5	A3-5	3	4	4	4	4	0
Embodiment 3-1-6	A3-6	3	4	4	4	4	0
								Embodiment 3-1-7	A3-7	3	4	4	4	4	0
Embodiment 3-1-8	A3-8	3	4	4	4	4	0
								Embodiment 3-1-9	A3-9	3	4	4	4	4	0
Embodiment 3-1-10	A3-10	3	4	4	4	4	0
								Embodiment 3-1-11	A3-11	3	4	4	4	4	0
Embodiment 3-1-12	A3-12	3	4	4	4	4	0
								Embodiment 3-1-13	A3-13	3	4	4	4	4	0
Embodiment 3-1-14	A3-14	3	4	4	4	4	0
								Embodiment 3-1-15	A3-15	3	4	4	4	4	0
Embodiment 3-1-16	A3-16	3	4	4	4	4	0
								Embodiment 3-1-17	A3-17	3	4	4	4	4	0
Embodiment 3-1-18	A3-18	3	4	4	4	4	0
								Embodiment 3-1-19	A3-19	3	4	4	4	4	0
Embodiment 3-1-20	A3-20	3	4	4	4	4	0
								Embodiment 3-1-21	A3-21	3	4	4	4	4	0
Embodiment 3-1-22	A3-22	3	4	4	4	4	0
								Embodiment 3-1-23	A3-23	3	4	4	4	4	0
Embodiment 3-1-24	A3-24	3	4	4	4	4	0
								Embodiment 3-1-25	A3-25	3	4	4	4	4	0
Embodiment 3-1-26	A3-26	3	4	4	4	4	0
								Embodiment 3-1-27	A3-27	3	4	4	4	4	0
Embodiment 3-1-28	A3-28	3	4	4	4	4	0
								Comparative example 3-1-1	A3-29	2	1	1	1	3	1
Comparative example 3-1-2	A3-30	2	1	2	2	3	1

(embodiment 3-2-1)

Except millbase A3-1 being changed into B3-1, obtain ink for inking in the same manner with embodiment 3-1-1.Viscosity is 18mPas.

In addition, carry out ink-vapor recording in the same manner, estimate with embodiment 3-1-1.The results are shown in table 19.

(embodiment 3-2-2～3-2-25 and comparative example 3-2-1 and 3-2-2)

Except millbase B3-1 being changed into the millbase shown in the table 19, obtain ink for inking in the same manner with embodiment 3-2-1.Viscosity is 17～22mPas.

Table 19

	The millbase of using	Solidified nature	Stability	Spray row property A	Spray row property B	Flexibility	Adhesivity
								Embodiment 3-2-1	B3-1	3	4	4	4	4	0
Embodiment 3-2-2	B3-2	3	4	4	4	4	0
								Embodiment 3-2-3	B3-3	3	4	4	4	4	0
Embodiment 3-2-4	B3-4	3	4	4	4	4	0
								Embodiment 3-2-5	B3-5	3	4	4	4	4	0
Embodiment 3-2-6	B3-6	3	4	4	4	4	0
								Embodiment 3-2-7	B3-7	3	4	4	4	4	0
Embodiment 3-2-8	B3-8	3	4	4	4	4	0
								Embodiment 3-2-9	B3-9	3	4	4	4	4	0
Embodiment 3-2-10	B3-10	3	4	4	4	4	0
								Embodiment 3-2-11	B3-11	3	4	4	4	4	0
Embodiment 3-2-12	B3-12	3	4	4	4	4	0
								Embodiment 3-2-13	B3-13	3	4	4	4	4	0
Embodiment 3-2-14	B3-14	3	4	4	4	4	0
								Embodiment 3-2-15	B3-15	3	4	4	4	4	0
Embodiment 3-2-16	B3-16	3	4	4	4	4	0
								Embodiment 3-2-17	B3-17	3	4	4	4	4	0
Embodiment 3-2-18	B3-18	3	4	4	4	4	0
								Embodiment 3-2-19	B3-19	3	4	4	4	4	0
Embodiment 3-2-20	B3-20	3	4	4	4	4	0
								Embodiment 3-2-21	B3-21	3	4	4	4	4	0
Embodiment 3-2-22	B3-22	3	4	4	4	4	0
								Embodiment 3-2-23	B3-23	3	4	4	4	4	0
Embodiment 3-2-24	B3-24	3	4	4	4	4	0
								Embodiment 3-2-25	B3-25	3	4	4	4	4	0
Comparative example 3-2-1	B3-26	2	1	1	1	3	1
								Comparative example 3-2-2	B3-27	2	1	2	2	3	1

(embodiment 3-3-1)

Except millbase A3-1 being changed into millbase C3-1, obtain ink for inking in the same manner with embodiment 3-1-1.Viscosity is 19mPas.

In addition, carry out ink-vapor recording in the same manner, estimate with embodiment 3-1-1.The results are shown in table 20.

(embodiment 3-3-2～3-3-25 and comparative example 3-3-1 and 3-3-2)

Except millbase C3-1 being changed into the millbase shown in the table 20, obtain ink for inking in the same manner with embodiment 3-3-1.Viscosity is 17～22mPas.

Table 20

	The millbase of using	Solidified nature	Stability	Spray row property A	Spray row property B	Flexibility	Adhesivity
								Embodiment 3-3-1	C3-1	3	4	4	4	4	0
Embodiment 3-3-2	C3-2	3	4	4	4	4	0
								Embodiment 3-3-3	C3-3	3	4	4	4	4	0
Embodiment 3-3-4	C3-4	3	4	4	4	4	0
								Embodiment 3-3-5	C3-5	3	4	4	4	4	0
Embodiment 3-3-6	C3-6	3	4	4	4	4	0
								Embodiment 3-3-7	C3-7	3	4	4	4	4	0
Embodiment 3-3-8	C3-8	3	4	4	4	4	0
								Embodiment 3-3-9	C3-9	3	4	4	4	4	0
Embodiment 3-3-10	C3-10	3	4	4	4	4	0
								Embodiment 3-3-11	C3-11	3	4	4	4	4	0
Embodiment 3-3-12	C3-12	3	4	4	4	4	0
								Embodiment 3-3-13	C3-13	3	4	4	4	4	0
Embodiment 3-3-14	C3-14	3	4	4	4	4	0
								Embodiment 3-3-15	C3-15	3	4	4	4	4	0
Embodiment 3-3-16	C3-16	3	4	4	4	4	0
								Embodiment 3-3-17	C3-17	3	4	4	4	4	0
Embodiment 3-3-18	C3-18	3	4	4	4	4	0
								Embodiment 3-3-19	C3-19	3	4	4	4	4	0
Embodiment 3-3-20	C3-20	3	4	4	4	4	0
								Embodiment 3-3-21	C3-21	3	4	4	4	4	0
Embodiment 3-3-22	C3-22	3	4	4	4	4	0
								Embodiment 3-3-23	C3-23	3	4	4	4	4	0
Embodiment 3-3-24	C3-24	3	4	4	4	4	0
								Embodiment 3-3-25	C3-25	3	4	4	4	4	0
Comparative example 3-3-1	C3-26	2	1	1	1	3	1
								Comparative example 3-3-2	C3-27	2	1	2	2	3	1

(embodiment 3-4)

Use is estimated the color reproduction of printed images by the characteristic printing ink that colored ink and embodiment 3-1-1, embodiment 3-2-1 and embodiment 3-3-1 obtain.

The dotted line of Fig. 3 represents to use the color reproduction (a of the printed images that the printing ink group obtains ^*, b ^*) maximum region, the characteristic printing ink that described printing ink group adds in above-mentioned colored ink by green, purple and the orange ink of embodiment 3-1-1, embodiment 3-2-1 and embodiment 3-3-1 preparation forms.

As a result, it is evident that, even present colored ink be difficult to the tone of color reproduction also can color reproduction.

Claims (10)

1. an ink composition for ink jet is characterized in that, contains: present at least a of orange, purple or green pigment dyestuff; Be selected from least a in the polymkeric substance of the monomeric macromolecular compound that comes from following formula (1-1) expression, the monomeric macromolecular compound that comes from following formula (2-1) expression and following formula (3-1) expression; And active radiation-curable compound,

In the described formula (1-1), R ¹The alkyl of expression hydrogen atom, replacement and unsubstituted alkyl any, R ²The expression alkylidene group, W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-and phenylene is any, X represents-CO-,-NHCO-,-OC (=O)-,-CH (OH) CH ₂-and-SO ₂-any, R ³, R ⁴Expression monovalence substituting group, R ³And R ⁴Can interconnection formation ring texture, m, n are respectively 0 or 1 independently,

In the described formula (2-1), R ¹The alkyl of expression hydrogen atom, replacement and unsubstituted alkyl any, R ²The expression alkylidene group, W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-and phenylene is any, X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OC (=O) NH-,-CO-,-SO ₂-,-CH (OH) CH ₂NH-,-CH (OH) CH ₂S-,-SO2NH-and-NHCO-any, Y represents-NR ⁵-,-O-and-S-any, R ⁵Represent any of hydrogen atom, alkyl and aryl, R ³, R ⁴Expression monovalence substituting group, R ³And R ⁴Can interconnection formation ring texture, m, n are respectively 0 or 1 independently,

In the described formula (3-1), R ¹Organic linking group of expression (m+n) valency, R ²Expression singly-bound or the organic linking group of divalent, A ¹Expression contains by being selected from the 1 valency organic group that organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, carbonatoms are at least a pigment adsorption structure that constitutes in alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl more than 4, n A1, R2 can distinguish identical or different independently, m represents 1～8, n represents 2～9, m+n is 3～10, P1 represents polymer backbone, m P ¹Can be identical or different.

2. ink composition for ink jet as claimed in claim 1, the monomer of wherein said formula (1-1) expression is the monomer of following formula (1-2) expression,

In the described formula (1-2), R ³, R ⁴Expression monovalence substituting group, R ³And R ⁴Can interconnection formation ring texture.

3. ink composition for ink jet as claimed in claim 1, the monomer of wherein said formula (2-1) expression is the monomer of following formula (2-2) expression,

In the described formula (2-2), R ¹The alkyl of expression hydrogen atom, replacement and unsubstituted alkyl any, Y, Z be expression-NR independently respectively ⁵-,-O-and-S-any, R ⁵Represent any of hydrogen atom, alkyl and aryl, R ³, R ⁴Expression monovalence substituting group, R ³And R ⁴Can interconnection formation ring texture.

4. ink composition for ink jet as claimed in claim 1, the polymkeric substance of its Chinese style (3-1) expression is the polymkeric substance of following formula (3-2) expression,

In the described formula (3-2), R ³Organic linking group of expression (m+n) valency, R ⁴, R ⁵Represent the organic linking group of singly-bound or divalent independently of one another, A ²Expression contains by being selected from the 1 valency organic group that organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups, carbamate groups, the group with coordination Sauerstoffatom, carbonatoms are at least a pigment adsorption structure that constitutes in alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl more than 4, n A ², R ⁴Can distinguish identical or differently independently, m represents 1～8, and n represents 2～9, and m+n is 3～10, P ²The expression polymer backbone, m P ², R ⁵Can distinguish identical or different independently.

5. ink composition for ink jet as claimed in claim 1, wherein for described polymkeric substance, in the described formula (3-2), P ²The polymer backbone of expression is to come from least a skeleton that is selected from polymer of vinyl monomer or multipolymer, ester based polymer, ether based polymer, carbamate based polymer, acid amides based polymer, epoxy based polymer, siloxane-based polymers and their modifier or the multipolymer.

6. ink composition for ink jet as claimed in claim 1, wherein said pigment dyestuff are to be selected from least a in the group shown below:

C.I. pigment orange 36,38,43,71;

C.I. pigment Violet 23,32,37,39; And

C.I. pigment Green 7,36,37.

7. ink composition for ink jet as claimed in claim 1, wherein said pigment dyestuff are following formula (A) expression De dioxazine type compounds,

In the described formula (A), R ¹～R ¹⁰Represent hydrogen atom, halogen atom or 1 valency group respectively independently, described halogen atom is fluorine atom, chlorine atom, bromine atoms, iodine atom.

8. an ink jet recording method is characterized in that, comprises following operation: (A ¹) operation of the ink composition for ink jet of spray row's claim 1-7 described in any one on printing medium; And (b ¹) shine active radioactive rays to spray row's ink composition for ink jet, make this ink composite solidified operation.

9. ink jet recording method as claimed in claim 8, wherein said active radioactive rays are to be the scope of 350～420nm and to produce the highest illumination on the printing medium surface be 10～2000mW/cm by the glow peak wavelength ²The ultraviolet ray of ultraviolet photodiode irradiation.

10. print, it carries out record by the described ink jet recording method of claim 8.

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