CN102002283A - Inkjet recording ink - Google Patents

Inkjet recording ink Download PDF

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Publication number
CN102002283A
CN102002283A CN 201010592959 CN201010592959A CN102002283A CN 102002283 A CN102002283 A CN 102002283A CN 201010592959 CN201010592959 CN 201010592959 CN 201010592959 A CN201010592959 A CN 201010592959A CN 102002283 A CN102002283 A CN 102002283A
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China
Prior art keywords
ink
weight
pigment
weight parts
inkjet recording
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CN 201010592959
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Chinese (zh)
Inventor
矢竹正弘
增田基城
伊东淳
黄木康弘
林广子
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Seiko Epson Corp
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Seiko Epson Corp
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Priority claimed from JP2004307763A external-priority patent/JP4853606B2/en
Priority claimed from JP2005094819A external-priority patent/JP4715271B2/en
Priority claimed from JP2005094820A external-priority patent/JP4687188B2/en
Priority claimed from JP2005094818A external-priority patent/JP4687187B2/en
Priority claimed from JP2005094813A external-priority patent/JP4715270B2/en
Priority claimed from JP2005292142A external-priority patent/JP2007099920A/en
Priority claimed from JP2005292140A external-priority patent/JP2007099918A/en
Priority claimed from JP2005292141A external-priority patent/JP4862341B2/en
Priority claimed from JP2005292145A external-priority patent/JP2007099923A/en
Priority claimed from JP2005292144A external-priority patent/JP2007099922A/en
Application filed by Seiko Epson Corp filed Critical Seiko Epson Corp
Publication of CN102002283A publication Critical patent/CN102002283A/en
Pending legal-status Critical Current

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Abstract

The invention provides an inkjet recording ink having excellent storage stability and ejection stability, while achieving good color development on plain paper or glossy paper and high gloss on glossy paper. The inkjet recording ink contains water and a pigment dispersed therein by using a polymer having at least 50 wt.% of benzyl acrylate and below 15wt.% of (meth)acrylic acid and the yellow pigment is PY74, the red pigment is selected from at least one kind of pV19, PR122, PR177 and PR 254 or the cyan pigment is PB15:1.

Description

Ink for inkjet recording
The application divides an application, the application number of its female case application: PCT/JP2005/019513 (200580036096.6), the applying date: 2005.10.24, denomination of invention: ink for inkjet recording
Technical field
The present invention relates to have the ink for inkjet recording of storage stability and ejection stability, the high Chromaticity in common paper or glossy paper and the high-luster in the glossy paper, good excellent characteristic such as photostabilization; The pigment dispersion that this ink for inkjet recording is used; Their manufacture method; Ink jet recording method etc.
Background technology
As ink for inkjet recording in the past, use dyestuff as the look material more, and used the ink of pigment also to begin to popularize.For example, open in the flat 1-301760 communique the spy, record this used in the ink of pigment as with colo(u)rant dispersion in water method and use the method for tensio-active agent.In addition, in the fair 5-064724 communique of spy, record use and have the dispersed polymeres of hydrophobic portion and hydrophilic portion its dispersive method.In addition, open in the flat 10-140065 communique, also studied the method that the surface of pigment is covered with polymer, studied the method for utilizing Phase inversion emulsification reaction or acid-precipitation method as its example the spy.
But, owing to all be to use with the polymkeric substance of vinylbenzene, therefore not too have stationarity as the main composition composition as the method for dispersed color, xanthochromia takes place in the secular preservation of print easily.In addition, in normal circumstances, when in ink, existing tensio-active agent or second glycol ether etc. to have the material of hydrophilic portion and hydrophobic portion, then cause the adsorption desorption of polymkeric substance easily, thereby the problem of the storage stability difference of ink is arranged.Water-base ink in the past needs tensio-active agent or second glycol ether etc. to have the material of hydrophilic portion and hydrophobic portion in order to reduce the leakage profit to paper.In the ink that does not use these materials, will be not enough to the impregnability of paper, make the paper kind be restricted, cause easily the problem of the reduction of print image quality thereby have in order to print uniformly.
In addition, in pigment dispersion in the past, for example when the additive (acetylenediol, acetylene alcohol, silicon class tensio-active agent, two (three) ethylene glycol monobutyl ethers or 1 that are used to improve print quality, 2-alkylene glycol or their mixture) time, then can't obtain secular storage stability, for the situation of paint ink, because poorly soluble again, therefore blocking problem in the nozzle of ink gun easily with regard to having ink dried; Erosion material such as used caking agent and bonding strength is reduced in constituting the material of shower nozzle, thus make problem such as ejection bad stability.
In addition, this kind residued in the ink system by the remnant of general dispersion agent dispersive pigment because of dispersion agent, and dispersion agent can't participate in fully disperseing and break away from pigment, thus the problem that has viscosity to uprise.When viscosity uprised, the addition of pigment isochrome material just was restricted, and particularly can't obtain the problem of enough print qualities in common paper in addition.
Particularly in paint ink, because the look material just disperses and does not dissolve, therefore guaranteeing of ejection stability and reliability is exactly to compare project even more important in dye ink, wherein consider, proposed various methods in the past from the viewpoint that realizes printing quality and stable two aspects of ejection simultaneously.Specifically, can enumerate: use with the acidic group of dispersion resin 60 moles more than the % with the method for alkaline neutralizing agent neutral resin (with reference to the spy open flat 08-183920 communique, the spy opens flat 09-040895 communique); Use acetylenediol type tensio-active agent and alkylol cpd method (with reference to the spy open flat 04-239068 communique, the spy opens flat 06-322307 communique); Contain and the surface of pigments reactant of the multipolymer of bonded functional group and ionic monomer and hydrophobic monomer chemically, also contain the method (spy opens the 2004-300370 communique) of the polymkeric substance that constitutes by (methyl) alkyl acid esters etc. with alkylene oxide chain.But, these methods hinder the dispersiveness of dispersion agent sometimes because of choice of Solvent, reduce the storage stability of composition for ink, in addition, in any document, all do not have record about the glossiness on the glossy paper, realize on glossiness and the stable two aspect this point of ejection also insufficient in fact at the same time.In addition, though be solvent at ink, open in the 2005-154548 communique the spy, about comprising 1, the ink of 2-alkylene glycol and gylcol ether, provide by making up with nonionic surfactant again and reduced the method that can realize duplex printing to the leakage of common paper profit, however in the document not about the record of addition and ejection stability problem, and in fact sometimes because of the different reductions (basic VIII) that cause spraying stability of addition.
In addition, to ink-jet paint ink in the past, studied: the use dissolver is with pigment and polymers soln mixing and carry out premix, utilizes and has used the stirring ball mill that is mixed with zirconic oxide compound slip medium to come dispersive method (with reference to the special 2004-535508 of showing communique); Pigment and polymers soln are passed filled the diverting device of zirconium white pearl and dispersive method (opening the 2004-217916 communique) in a looping fashion with reference to the spy; Perhaps with method (opening the 2003-176431 communique) of handling with miniature fluidizer behind pigment and the polymers soln premix etc. with reference to the spy.But, dispersion machines such as use ball mill (beads mill), sand mill or ball mill in the past the ink-jet situation with paint ink, in dispersing of pigments, were proposed after the mixing of common whipping appts or dissolver etc.Yet, in this method, produced inorganic pollutent, the bad stability when therefore making ink-jet with paint ink owing to medium physically destroys.In order to reduce aforesaid pollutent, studied and used high-pressure homogenizer to carry out the way of dispersing of pigments.(with reference to special fair 8-30158 communique).According to this method,, therefore can improve the stability when making ink-jet with paint ink because the generation of pollutent is suppressed.But, since low in this treatment condition down cut speed, so stability is still abundant inadequately.
In addition, in can the ink-jet recording device of printing color image, as the recording method that forms black, can mainly enumerate three following methods, that is, (1) overlaps color inks and utilizes three and look or the many and look more than it, shows the method (synthetic black) of black; (2) possess the India ink that constitutes by the solvent identical, apply the method for India ink with picture black, coloured image both sides with color inks; (3) pay attention to the text printing, possess the India ink more weak than color inks power of impregnation, in picture black and text printing, form India ink, in coloured image, utilize color inks to form synthetic black method, yet situation for (1), if used the foregoing ink that utilizes general dispersion agent dispersive pigment, then owing to ink droplet is overlapped a plurality of, therefore can cause by the glossiness on the glossy paper and reduce, the printing quality that infiltration on the common paper etc. causes reduces, when when suppressing these phenomenons and reduce applied amount, then have the problem of the reduction that causes color emissivity in addition.For the situation of (3), the black in the coloured image forms also identical with (1), and identical problem is arranged.In addition, under the situation of (2),, that is, in the text printing on common paper, be difficult to the problem that obtains enough color emissivities, infiltrates easily just like inferior problem; In addition, because different, therefore can cause tone offsetting (level is clear inadequately) in interface with the grey that forms by color inks etc. with the tone of the black that forms by color inks; Because glossiness changes sharp in the part of black, therefore can cause luster mottlings.
In addition, paint ink is compared with dye ink, though it is good aspect various weathering resistances such as photostabilization or anti-gaseousness, water tolerance, yet in yellow ink, for C.I. Pigment Yellow 73 74 of general frequent use in the past etc., have aspect photostabilization and to compare the relatively poor problem of ability with cyan or magenta.On the other hand, as the good yellow ultramarine of photostabilization, known in the past have C.I. pigment yellow 13 8, however consider color emissivity low, as the not good situation of the storage stability of ink, and be not suitable in the ink for inkjet recording.So, in the ink for inkjet recording that has used yellow ultramarine, as for the purpose that realizes this two aspect such as all characteristics such as photostabilization and printing quality, storage stability etc. simultaneously, and be used for C.I. pigment yellow 13 8 is used for ideally the means of ink for inkjet recording, adopted following method etc. in the past, promptly, by pigment is covered with the organic high molecular compound with the anionic property base that has been neutralized, improve the method (spy opens flat 11-172180 communique) of water tolerance, photostabilization, tone and storage stability; By making up the method (spy opens flat 11-228888 communique) that obtains to have distinctness and images with high image quality and good sunproof print with recording medium with ink receiving layer of having implemented specific coating; By changing the miniaturization condition in the pigment manufacturing C.I. pigment yellow 13 8 is made as special crystal formation, forms the method (spy opens the 2002-105351 communique) of the good material that is suitable for ink-jet of the transparency and distinctiveness.But in any method, though the photostabilization of record thing is good, aspect color emissivity, particularly the color emissivity in the common paper can not be said so enough.In addition, also can't guarantee the glossiness on the glossy paper, still unsatisfactory aspect printing quality.Like this, in the ink for inkjet recording of yellow ultramarine, do not see the material that has photostabilization and printing quality two aspect characteristics ideally concurrently as yet as the look material.
Summary of the invention
The objective of the invention is to, the ink-vapor recording that can solve described problem composition, pigment dispersion and their manufacture method and ink jet recording method are provided.
The present invention can have following formation.
(I) feature of ink for inkjet recording of the present invention is, contain water and pigment, wherein pigment is to use following polymer dispersed, promptly, to the benzyl acrylate more than the major general 50 weight % and/or cyclohexyl acrylate, (methyl) acroleic acid polymerization below the 20 weight %, and this polymkeric substance has the following acid number of the above 150mgKOH/g of 30mgKOH/g as the constituent of polymkeric substance.In addition, the weight-average molecular weight of described polymkeric substance can be made as more than 20000 below 200000.In addition, in this ink, can contain the above 1 weight % of 0.05 weight % following be selected from 2,4,7,9-tetramethyl--5-decine-4,7-glycol, 3,6-dimethyl-4-octyne-3,6-glycol, 2,4,7,9-tetramethyl--5-decine-4, the alkylene oxide affixture of 7-glycol (alkylene oxideadduct) and 3,6-dimethyl-4-octyne-3, more than one in the alkylene oxide affixture of 6-glycol.Ink for inkjet recording of the present invention has following effect,, can provide storage stability and ejection excellent in stability that is, has the high Chromaticity in common paper or the glossy paper and the ink for inkjet recording of the high-luster in the glossy paper concurrently.
(II) feature of ink for inkjet recording of the present invention is, contain water and pigment, wherein pigment is to use following polymer dispersed, promptly, to the benzyl acrylate more than the major general 50 weight %, (methyl) acroleic acid polymerization below the 15 weight %, and this polymkeric substance has the following acid number of the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight more than 20000 below 120000 as the constituent of polymkeric substance.Ink for inkjet recording of the present invention has following effect,, can provide storage stability and ejection excellent in stability that is, has the high Chromaticity in common paper or the glossy paper and the ink for inkjet recording of the high-luster in the glossy paper concurrently.
(III) feature of ink for inkjet recording of the present invention is, be to contain the ink for inkjet recording that water and pigment form, wherein pigment is to use following polymer dispersed, promptly, as the constituent of polymkeric substance to the benzyl acrylate more than the major general 50 weight %, (methyl) acroleic acid polymerization that 15 weight % are following, and this polymkeric substance has the following acid number of the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight is more than 20000 below 120000, described pigment is PY74 as yellow ultramarine, as magenta pigment is to be selected from PV19, PR122, more than at least a among PR177 and the PR254, or be PB15:1 as green pigment.In this ink for inkjet recording, below the above 110nm of the preferred 90nm of dispersion particle diameter of described yellow ultramarine, and below the above 80nm of the preferred 30nm of one-level particle diameter, in addition, below the above 100nm of the preferred 20nm of dispersion particle diameter of described magenta pigment, and below the above 70nm of the preferred 20nm of one-level particle diameter, in addition, below the above 100nm of the preferred 20nm of dispersion particle diameter of described green pigment, and below the above 70nm of the preferred 20nm of one-level particle diameter.In addition, according to (III), a kind of ink group also is provided, be to have yellow ink at least, the ink group of magenta ink and cyan, described each ink contains water and pigment, wherein pigment is to use following polymer dispersed, promptly, as the constituent of polymkeric substance to the benzyl acrylate more than the major general 50 weight %, (methyl) acroleic acid polymerization that 15 weight % are following, and this polymkeric substance has the following acid number of the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight is more than 20000 below 120000, and the contained pigment of described yellow ink is PY74, the contained pigment of magenta ink is to be selected from PV19, PR122, more than at least a among PR177 and the PR254, the contained pigment of cyan is PB15:1.Ink for inkjet recording of the present invention has following effect,, can provide storage stability and ejection excellent in stability that is, has the high Chromaticity in common paper or the glossy paper and the ink for inkjet recording of the high-luster in the glossy paper concurrently.
(IV) feature of ink for inkjet recording of the present invention is, at least contain the following TriMethylolPropane(TMP) of the above 20 weight % of water, pigment and 1 weight %, wherein pigment is to use following polymer dispersed, promptly, to the benzyl acrylate more than the major general 50 weight %, (methyl) acroleic acid polymerization below the 15 weight %, and this polymkeric substance has the following acid number of the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight more than 20000 below 120000 as the constituent of polymkeric substance.Ink of the present invention has following effect,, can provide storage stability and ejection excellent in stability that is, has the high Chromaticity in common paper or the glossy paper and the ink for inkjet recording of the high-luster in the glossy paper concurrently.In addition, the present invention has the effect of the ink for inkjet recording that can provide following, promptly, stop up the accumulation of Restoration and ink and suppress respond well, and in the boundless printing on printed mediums such as postcard, can not be accompanied by drying and pile up the situation of the printed medium of making dirty by the interior ink of beating of throwing of oriented ink-jet recording device.
(V) feature of ink for inkjet recording of the present invention is, at least contain the following 2-butyl-2-ethyl-1 of the above 10 weight % of water, pigment and 0.1 weight %, ammediol, wherein pigment is to use following polymer dispersed, promptly, to the benzyl acrylate more than the major general 50 weight %, (methyl) acroleic acid polymerization below the 15 weight %, and this polymkeric substance has the following acid number of the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight more than 20000 below 120000 as the constituent of polymkeric substance.Ink for inkjet recording of the present invention has following effect,, can provide storage stability and ejection excellent in stability that is, has the high Chromaticity in common paper or the glossy paper and the ink for inkjet recording of the high-luster in the glossy paper concurrently.
(VI) water that the invention provides blending dispersion, dispersion agent, the manufacture method of pigment and polymkeric substance and the pigment dispersion that forms at this this polymkeric substance of pigment particles finishing, it is characterized in that, this polymkeric substance has benzyl acrylate more than the 50 weight % at least as its constituent, (methyl) vinylformic acid that 15 weight % are following, and the acid number of this polymkeric substance is below the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight is more than 20000 below 120000, when this disperses, in the weight-average molecular weight of this polymkeric substance under the situation below 120000 more than 50000, disperseing dosage is more than the 95 weight % below the 300 weight % with respect to pigment, and in the weight-average molecular weight of this polymkeric substance is more than 20000 and under less than 50000 situation, and disperseing dosage is more than the 45 weight % and less than 180 weight % with respect to pigment.In addition, the invention provides a kind of pigment dispersion, it is characterized in that, utilize the manufacture method of described pigment dispersion to obtain.In addition, the invention provides a kind of composition for ink, it is characterized in that, contain described pigment dispersion.The manufacture method of pigment dispersion of the present invention can be provided for storage stability and ejection excellent in stability, and have high Chromaticity in common paper or the glossy paper and the pigment dispersion in the high-luster in the glossy paper and the fixed ink for inkjet recording concurrently, and can provide and contain the ink for inkjet recording that this pigment dispersion forms.
(VII) feature of ink for inkjet recording of the present invention is, it is the ink for inkjet recording that contains water and pigment, wherein pigment is to use following polymer dispersed, promptly, to the benzyl acrylate more than the major general 50 weight %, (methyl) acroleic acid polymerization below the 15 weight %, and acid number, the weight-average molecular weight of this polymkeric substance with 50～120mgKOH/g is more than 20000 below 120000 as the constituent of polymkeric substance; In addition, contain at least a of the resin particle that constitutes by following polymkeric substance with the form of resin emulsion, promptly, to the benzyl acrylate more than the major general 50 weight % and (methyl) acroleic acid polymerization below the 15 weight %, and acid number, the weight-average molecular weight of this polymkeric substance with 50～120mgKOH/g is more than 20000 below 120000 as the constituent of polymkeric substance.In this ink, used polymkeric substance preferably represents to use more than 50% and the identical polymkeric substance of the constituent polymkeric substance that uses as described pigment dispersing agent with the weight conversion ratio in the described resin emulsion, in addition, preferred 30～the 150nm of median size of the resin particle that contains as described resin emulsion, in addition, the resin particle that contains as described resin emulsion is preferably contained with 0.1～10 weight % with respect to the ink total amount.So the ink for inkjet recording of the present invention that forms has following effect,, can provide storage stability and ejection excellent in stability that is, has the high Chromaticity in common paper or the glossy paper and the ink for inkjet recording of the high-luster in the glossy paper concurrently.
(VIII) feature of ink for inkjet recording of the present invention is, at least constitute by the ink that contains water and pigment, wherein pigment is to use following polymer dispersed, promptly, as the constituent of polymkeric substance to the benzyl acrylate more than the major general 50 weight % and (methyl) acroleic acid polymerization below the 15 weight %, acid number with 50～120mgKOH/g, weight-average molecular weight are 20000～120000, and described ink for inkjet recording contains at least:
1) C of 0.5～15 weight % 4～C 101, the 2-alkylene glycol,
2) 5～30 weight % remove described 1, the C beyond the 2-alkylene glycol 10Following polyalcohols.In this ink, described 1, the content of 2-alkylene glycol and described polyalcohols and preferred 6～40 weight %, in addition, described 1,2-alkylene glycol and described polyalcohols contain preferred 1: 50～1: 1.5 scope of ratio, in addition, also preferably contain 0.5～15 weight % with R 1O-(C mH 2mO) n-R 2(m and n are the integer more than 1, m * n≤10, R 1And R 2Be C 8Following alkyl, R 1And R 2Both can be the same or different) expression gylcol ether.In addition, described 1 in this mode, 2-alkylene glycol and described gylcol ether contained ratio preferred 10: 1 :～1: 10 scope, described 1,7～40 weight % content of 2-alkylene glycol, described polyalcohols and described gylcol ether and preferred.Ink for inkjet recording of the present invention has following effect, promptly, can provide storage stability good, have high Chromaticity in common paper or the glossy paper and the high-luster in the glossy paper concurrently, and have high ejection stability and ejection reliability, can stably obtain the ink for inkjet recording of good print.
(IX) ink-jet of the present invention with the feature of paint ink is, use the pigment dispersion of following making, promptly, use pigment and have at least acid number below the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight is the polymkeric substance below 120000 more than 20000, in high-pressure homogenizer, carry out 3 and take turns more than (3passes) 8 and take turns following dispersion treatment and make with the processing pressure more than the 150MPa.In addition, ink-jet of the present invention with the feature of the manufacture method of paint ink is, described pigment and the polymers soln that becomes dispersion agent are carried out 3 with the processing pressure more than the 150MPa take turns above 8 and take turns following dispersion treatment in high-pressure homogenizer, mix with the vehicles composition by the pigment dispersion that will so make and make.The present invention has the effect that paint ink is used in the ink-jet that can provide following, that is, excellent in stability has high Chromaticity in common paper, high-luster is arranged in glossy paper, the ejection excellent in stability of the ink from ink gun.
(X) feature of ink for inkjet recording of the present invention is, contain water and pigment dispersion, wherein pigment dispersion is to form at the following polymkeric substance of self-dispersion type pigment particles finishing, promptly, as the constituent of polymkeric substance to the benzyl acrylate more than the major general 50 weight % and (methyl) acroleic acid polymerization below the 15 weight %, have the following acid number of the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight is more than 20000 below 120000.Ink for inkjet recording of the present invention has following effect,, can provide storage stability and ejection excellent in stability that is, has the high Chromaticity in common paper or the glossy paper and the ink for inkjet recording of the high-luster in the glossy paper concurrently.
(XI) ink jet recording method of the present invention is to use cyan at least, magenta, yellow trichromatic ink forms the tertiary colo(u)r(s) (third color) that comprises secondary look (secondary color) and black, realize the ink jet recording method of coloured image and monochrome image, it is characterized in that, described ink is the ink for inkjet recording that contains water and pigment, wherein pigment is to use following polymer dispersed, promptly, as the constituent of polymkeric substance to the benzyl acrylate more than the major general 50 weight % and (methyl) acroleic acid polymerization below the 15 weight %, acid number with 50～120mgKOH/g, weight-average molecular weight is 20000～120000, and be by with described ink with cyan, magenta, xanchromatic applies in proper order, and formation comprises the tertiary colo(u)r(s) of black and realizes the record images method.In this recording method, both can use following ink-jet recording device to print, that is, the color alignment of printhead is vertical with the printing scanning direction of shower nozzle, and color sequences begins to be cyan, magenta, yellow from a side who applies early; Print in the time of also can using following ink-jet recording device only to scan in the outlet, that is, the color alignment of printhead is parallel with the printing scanning direction of shower nozzle, and puts in order and be cyan, magenta, yellow; Perhaps can also use the ink-jet recording device that puts in order to yellow, magenta, cyan, print when only scanning in the loop.Ink jet recording method of the present invention has following effect, that is, in the coloured image printing in common paper or glossy paper, even in comprising the tertiary colo(u)r(s) of black, also can realize high Chromaticity, in glossy paper, also have high-luster in addition concurrently, can obtain good print.
(XII) feature of ink for inkjet recording of the present invention is, it is the ink that contains water and pigment, wherein pigment is to use following polymer dispersed, promptly, to the benzyl acrylate more than the major general 50 weight % and (methyl) acroleic acid polymerization below the 15 weight %, have the acid number of 50～120mgKOH/g as the constituent of polymkeric substance, weight-average molecular weight is 20000～120000, as described pigment, use C.I. pigment yellow 13 8 at least.In this ink, as described pigment, also can also use C.I. Pigment Yellow 73 74, under this situation, C.I. pigment yellow 13 8 contains than the scope that also can be made as 20: 1～1: 10 with the weight conversion with C.I. Pigment Yellow 73 74.Ink for inkjet recording of the present invention is in the ink of yellow ultramarine as main look material, has following effect, promptly, storage stability and ejection excellent in stability can be provided, have high Chromaticity in common paper or the glossy paper and the high-luster in the glossy paper concurrently, can also obtain the ink for inkjet recording of the good record thing of photostabilization in addition.
(XIII) ink-jet of the present invention with the feature of the manufacture method of paint ink is, by pigment dispersion and the mixing of vehicles composition are made, wherein, pigment dispersion be with behind the synthetic dyestuff without the wet cake of this pigment of drying process, perhaps the pigment of powder shaped is mixed with water and with edge-runner mill or three roller runner millings disperse and this hybrid pigment and the polymers soln and the dispersant that become dispersion agent, in high-pressure homogenizer, carry out 3 and take turns above 8 and take turns following dispersion treatment and make with the processing pressure more than the 150MPa.The present invention has the effect that paint ink is used in the ink-jet that can provide following, that is, excellent in stability has high Chromaticity in common paper, high-luster is arranged in glossy paper, the ejection excellent in stability of the ink from ink gun.
(XIV) feature of ink for inkjet recording of the present invention is, contain water and pigment, wherein pigment is to use following polymer dispersed, promptly, as the constituent of polymkeric substance to the benzyl acrylate more than the major general 50 weight % and epoxy (methyl) acrylate more than the 10 weight % and/or (methyl) propenoic methyl carbamate, (methyl) acroleic acid polymerization below the 15 weight %, have the following acid number of the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight is more than 20000 below 120000.Ink for inkjet recording of the present invention has following effect,, can provide storage stability and ejection excellent in stability that is, has high Chromaticity and the high-luster in the glossy paper and fixed ink for inkjet recording in common paper or the glossy paper.
(XV) feature of the manufacture method of pigment dispersion of the present invention is, when the following polymkeric substance of pigment particles finishing, promptly, constituent as polymkeric substance has the benzyl acrylate more than the 50 weight %, (methyl) vinylformic acid below the 15 weight % at least, acid number is below the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight is utilized the not dispersion treatment of the high-pressure homogenizer of working medium more than 20000 below 120000.In addition, the feature of ink for inkjet recording of the present invention is to contain the pigment dispersion that so obtains.The ink for inkjet recording that contains the pigment dispersion that the manufacture method of utilizing pigment dispersion of the present invention obtains has following effect, promptly, storage stability and ejection excellent in stability have high Chromaticity in common paper or the glossy paper and the high-luster in the glossy paper concurrently.
(XVI) feature of ink for inkjet recording of the present invention is, contain water and pigment, wherein pigment is to use following polymer dispersed, promptly, as the constituent of polymkeric substance to the benzyl acrylate more than the major general 50 weight % and the styrene monomer more than the 10 weight % and/or vinylbenzene macromonomer, (methyl) acroleic acid polymerization below the 15 weight %, have the following acid number of the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight is more than 20000 below 120000.Ink for inkjet recording of the present invention has following effect,, can provide storage stability and ejection excellent in stability that is, has high Chromaticity and high-luster in the glossy paper and stationarity in common paper or the glossy paper.
(XVII) feature of ink for inkjet recording of the present invention is, contain water and pigment, wherein pigment is to use following polymer dispersed, promptly, as the constituent of polymkeric substance to the benzyl acrylate more than the major general 50 weight % and (methyl) alkyl acrylate more than the 10 weight % and/or (methyl) vinylformic acid alkylene diol ester, (methyl) acroleic acid polymerization below the 15 weight %, have the following acid number of the above 120mgKOH/g of 50mgKOH/g, weight-average molecular weight is more than 20000 below 120000.Ink for inkjet recording of the present invention has following effect,, can provide storage stability and ejection excellent in stability that is, has high Chromaticity and high-luster in the glossy paper and stationarity in common paper or the glossy paper.
Description of drawings
Fig. 1 is a sketch chart of having implemented ink-jet recording device of the present invention.
Fig. 2 is that the color alignment of ink nozzle is the nozzle arrangement figure of the printhead of extended spread.
Fig. 3 is that the color alignment of ink nozzle is one of the nozzle arrangement figure of the printhead of horizontally-arranged row.
Fig. 4 be the color alignment of ink nozzle be horizontally-arranged row printhead nozzle arrangement figure two.
Embodiment
Ink for inkjet recording of the present invention, pigment dispersion and their manufacture method and ink jet recording method are in view of being required just like inferior characteristic, promptly, at storage stability and spray aspect stable good, it on common paper or glossy paper high Chromaticity, on the glossy paper except having enough glossinesses, also have stationarity, good etc. aspect the ejection of the ink from ink gun stability, obtain according to the result of further investigation.
(ink for inkjet recording)
The ink for inkjet recording of the variety of way that is comprised among the present invention can contain water and pigment, wherein pigment is to use following polymer dispersed, promptly, as the constituent of polymkeric substance to the benzyl acrylate more than the major general 50 weight % and/or cyclohexyl acrylate, (methyl) acroleic acid polymerization below the 20 weight %, have the following acid number of the above 150mgKOH/g of 30mgKOH/g, preferably weight-average molecular weight is more than 20000 below 200000.
(component of polymer)
Among the present invention, also can use as the constituent polymerization of polymkeric substance cyclohexyl acrylate and/or benzyl acrylate and (methyl) polymerizing acrylic acid thing below the 20 weight % more than the 50 weight %.If because cyclohexyl acrylate and/or benzyl acrylate be less than 50 weight %, stationarity reduces, so their preferable range is more than 50 weight %, yet do not negate the situation less than 50 weight %.So, more than the preferred 50 weight %, more preferably more than the 60 weight %, further more than the preferred 70 weight %.In addition, preferably with (methyl) polymerizing acrylic acid below the 20 weight %, yet when surpassing 20 weight %, then the color emissivity of ink for ink-jet print in common paper has the tendency of reduction, but do not negate the polymerization that surpasses 20 weight %, but the scope that provides as preferred scope, preferred scope is below the 10 weight %.In addition, when comparing methacrylic acid and vinylformic acid, consider more preferably to use vinylformic acid from fixed viewpoint.
In addition, among the present invention, for example as the ink for inkjet recording of (II), as the constituent of polymkeric substance preferably with the benzyl acrylate more than the 50 weight %, (methyl) acroleic acid polymerization below the 15 weight %.If benzyl acrylate is less than 50 weight %, then owing to stationarity reduces, so preferred range does not still negate the situation less than 50 weight % more than 50 weight %.So, more than the preferred 50 weight %, more preferably more than the 60 weight %, further more than the preferred 70 weight %.In addition, preferably with (methyl) polymerizing acrylic acid below the 15 weight %.When surpassing 15 weight %, then the color emissivity of ink for ink-jet print in common paper just has the tendency of reduction, but do not negate the polymerization that surpasses 15 weight %, but the scope that provides as preferred range, preferred scope is below the 10 weight %.In addition, when comparing methacrylic acid and vinylformic acid, consider more preferably to use vinylformic acid from fixed viewpoint.
In addition, the weight-average molecular weight of the polymkeric substance of dispersed color is preferred more than 20000 below 200000 among the present invention.When weight-average molecular weight less than 20000 the time, then, when surpassing 200000, then there is viscosity to uprise as ink for ink-jet print as prolonged preservation stability, thermostability and the stationarity variation of ink for ink-jet print, the tendency of dispersion stabilization variation, the tendency that also has ejection stability to reduce in addition.More preferably below 120000.When surpassing 120000, then be difficult to obtain good dispersion stabilization.
In addition, among the present invention, for example,, can improve stationarity and glossiness by using epoxy (methyl) acrylate and/or (methyl) propenoic methyl carbamate more than the 10 weight % as the ink for inkjet recording of (XIV).If below the 10 weight %, then stationarity worsens.More preferably more than the 15 weight %.
Can use such epoxy (methyl) acrylate and/or (methyl) propenoic methyl carbamate.As the example of epoxy (methyl) acrylate and/or (methyl) propenoic methyl carbamate, can enumerate the material that in side chain, has epoxy (methyl) acrylate or (methyl) propenoic methyl carbamate.Material with epoxy (methyl) acrylate for example can be by in copolymerization on the material of (methyl) methyl acrylate and (methyl) glycidyl acrylate addition reaction (methyl) vinylformic acid obtain.In addition, material with (methyl) propenoic methyl carbamate for example can by in copolymerization on the material of (methyl) methyl acrylate and (methyl) vinylformic acid 2-hydroxy methacrylate, addition reaction is supportted the material that vulcabond or isophorone diisocyanate and (methyl) vinylformic acid 2-hydroxy methacrylate reacted with mol ratio 1 with toluene and is obtained.
In addition, as epoxy (methyl) acrylate, for example can enumerate the Resins, epoxy and (methyl) acrylic acid affixture such as glycidyl ether of bisphenol A type epoxy resin, bisphenol f type epoxy resin, cresols novolac epoxy resin, line style phenol aldehyde type epoxy resin, the poly-Tetraglycol 99 of polypropylene glycol etc.As (methyl) propenoic methyl carbamate, for example can enumerate the affixture of isocyanate prepolymer and hydroxy acryl acid ester, wherein, isocyanate prepolymer is by making polymeric polyisocyanate such as toluene support vulcabond, isophorone diisocyanate, hexamethylene diisocyanate and polypropylene glycol, SYNPERONIC PE/F68, polytetramethylene glycol, hexanodioic acid and ethylene glycol, glycol ether, 1,4-butyleneglycol, 1, polyol reaction such as the polycondensate of polyvalent alcohols such as 6-butyleneglycol, polycaprolactone and; The hydroxy acryl acid ester comprises (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid pentaerythritol ester, (methyl) vinylformic acid dipentaerythritol ester etc.
In addition; the polymerizable monomer of used having (methyl) acryl in the invention as (XIV); can enumerate simple function (methyl) acrylate or multifunctional (methyl) acrylate and their mixture; as simple function (methyl) acrylate, for example can enumerate (methyl) vinylformic acid 2-methoxy ethyl ester; (methyl) vinylformic acid 2-ethoxyethyl group ester; (methyl) vinylformic acid 2-phenoxy group ethyl ester; (methyl) vinylformic acid ethoxydiglycol ester; (methyl) vinylformic acid phenoxy group glycol ether ester; the ethylene oxide adduct of nonylphenol (methyl) acrylate; the propylene oxide adduct of nonylphenol (methyl) acrylate; (methyl) benzyl acrylate; (methyl) cyclohexyl acrylate; (methyl) vinylformic acid tetrahydro furfuryl ester; (methyl) vinylformic acid dicyclopentenyl ester; (methyl) isobornyl acrylate; (methyl) vinylformic acid two cyclopentenes oxygen base ethyl esters; (methyl) vinylformic acid 2-hydroxyl-3-phenoxy propyl ester; (methyl) vinylformic acid 2-hydroxyl ethyl ester; (methyl) vinylformic acid 2-hydroxypropyl acrylate etc.
In addition, among the present invention,, can use 10 weight % above styrene monomer and/or vinylbenzene macromonomer for example as the ink for inkjet recording of (XVI).By setting like this, just can improve stationarity and glossiness.If below the 10 weight %, then stationarity worsens.More preferably more than the 15 weight %.
In addition, among the present invention,, can use (methyl) alkyl acrylate and/or (methyl) vinylformic acid alkylene diol ester more than 10% for example as the ink for inkjet recording of (XVII).By setting like this, just can improve stationarity and glossiness.If below 10%, then stationarity worsens.More preferably more than 15%.As the example of (methyl) alkyl acrylate and/or (methyl) vinylformic acid alkylene diol ester, can enumerate branched ester, (methyl) vinylformic acid (single, two, three, four) glycol ester, (methyl) vinylformic acid PEG (200,400,600,1000) ester, (methyl) vinylformic acid (single, two, the three) propylene glycol ester of (methyl) vinylformic acid C1～C20 alkyl or C4～C20 etc.
As the polymeric method of various polymkeric substance used among the present invention,, can use alcoholic solvent, ketones solvent, ether solvent, gylcol ether as solvent.But,, therefore need to remove described solvent in the back owing to be the colo(u)rant dispersion of water class.So,, can use solvent as follows as this kind solvent.As described alcoholic solvent, can enumerate methyl alcohol, ethanol, Virahol, 1-butanols, the trimethyl carbinol, isopropylcarbinol, Pyranton etc.As described ketones solvent, can enumerate acetone, methyl ethyl ketone, metacetone, methyl iso-butyl ketone (MIBK), pimelinketone etc.In addition, as described ether solvent, can enumerate dibutyl ether, tetrahydrofuran (THF), dioxane etc.In addition, as described gylcol ether, can enumerate ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl carbitol, ethylene glycol butyl ether etc.
In addition, as the radical polymerization initiator that is used for polymer polymerizing, can use organo-peroxides such as t-butylperoxy (2-ethylhexanoate), two-tert-butyl peroxide, t-butylperoxy benzoic ether, t-butylperoxy octanoate; 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), dimethyl-2, the two butyric esters, 2 of 2 '-azo, the two azo-compounds such as (2-methylbutyronitriles) of 2 '-azo etc.; Potassium Persulphate, Sodium Persulfate etc., however be not limited to them, so long as can realize the material of radical polymerization, also can use described initiator in addition.The usage quantity of radical polymerization initiator in polymerization the used monomer preferred 0.01 mole more than the % 5 moles below the %.Though described polymeric temperature is not particularly limited, as a rule be 30～100 ℃ scope, preferred 40～90 ℃ scope.When polymerization temperature is too low, in monomeric polymerization, just need for a long time, according to circumstances different, might reduce and remaining a large amount of monomer by percent polymerization.
Among the present invention in dispersing of pigments used polymkeric substance can not have under the effect yet, will be selected from more than one combinations in commercially available vinylbenzene-(methyl) acrylic copolymer, vinylbenzene-(methyl) vinylformic acid-(methyl) acrylate copolymer, (methyl) polyalkylene glycol acrylate ester-(methyl) acrylic copolymer, vinyl-acetic ester-maleic acid, the styrene-maleic acid copolymer etc. and use.But, preferably be the polymkeric substance that utilizes acrylate and acrylic acid copolymerization to obtain more than at least 80 weight %.As this acrylate, can use methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, Ethyl acrylate, cyclohexyl acrylate, Octyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, vinylformic acid 2-ethylhexyl carbitol ester, vinylformic acid phenol EO sex change ester, N-vinyl pyrrolidone, isobornyl acrylate, benzyl acrylate, vinylformic acid to cumyl phenol EO sex change ester, vinylformic acid 2-hydroxyethyl-commercially available acrylate such as 3-phenoxy propyl ester.In addition, can substitutional crylic acid, and use ω-carboxyl-polycaprolactone single-acrylate, phthalandione monohydroxy ethyl propylene acid esters, acrylic acid dimer etc.
In addition, among the present invention, for example as the ink for inkjet recording of the invention of (VII), can be in ink also contain at least a of the resin particle that constitutes by following polymkeric substance with the form of resin emulsion, promptly, with the benzyl acrylate more than the 50 weight % and (methyl) acroleic acid polymerization below the 15 weight %, have the acid number of 50～120mgKOH/g as the constituent of polymkeric substance, weight-average molecular weight is 20000～120000.By setting like this, just can guarantee storage stability and spray under the state good aspect stable, obtain higher color emissivity on common paper and the glossy paper and high-luster and the stationarity on the glossy paper.As the means that improve color emissivity and glossiness, the method that the usage quantity that improves dispersion agent used in the colo(u)rant dispersion is arranged, yet when the usage rate as dispersion agent becomes too high, the viscosity that then might cause stopping up reduction, the ink of Restoration rises and the reduction of the ejection reliability that accompanies with it, and is therefore not ideal enough.Different with it, contain in form under the situation of the resin particle that constitutes by described polymkeric substance with resin emulsion, can not cause the reduction of aforesaid ejection reliability, can improve color emissivity and glossiness effectively.In addition, by adding described resin emulsion, can also obtain to improve the effect of the weathering resistance (photostabilization, anti-gaseousness) of ink.In the invention of (VII), the polymkeric substance that the polymkeric substance that constitutes resin particle contained in the described resin emulsion preferably forms the benzyl acrylate more than the 50 weight % and (methyl) acroleic acid polymerization below the 15 weight %.If benzyl acrylate is less than 50 weight %, because stationarity reduces, so preferred range is more than 50 weight %, yet do not negate the situation less than 50 weight %.Though more than the preferred 50 weight % of benzyl acrylate, yet more preferably more than the 60 weight %, further more than the preferred 70 weight %.In addition, preferably with (methyl) polymerizing acrylic acid below the 15 weight %.When surpassing 15 weight %, just have the tendency that the color emissivity of ink for ink-jet print in common paper reduces, yet do not negate the situation that surpasses 15 weight %, preferred scope is below the 10 weight %.In addition, when comparing methacrylic acid and vinylformic acid, consider more preferably to use vinylformic acid from fixed viewpoint.In the invention of (VII), described resin emulsion is under the situation of yellow pigment in addition at the main composition look material of ink, from storage stability and ejection excellent in stability are provided, the viewpoint that has the ink for inkjet recording of high luminous in common paper or the glossy paper and the high-luster in the glossy paper concurrently considers, the preferred resin particle that uses the polymkeric substance by the acid number with 50mg～80mgKOH/g to constitute.If less than the acid number of 50mgKOH/g, then can cause the reduction of dispersing of pigments stability, if surpass the acid number of 80mgKOH/g, then the color emissivity in the common paper will reduce.Preferred acid number is 50～70mgKOH/g.
In addition, for example in the invention of (VII), main composition look material at ink is under the situation of yellow ultramarine, high Chromaticity from realize common paper or glossy paper and the high-luster in the glossy paper, fixed viewpoint consider, the preferred resin particle that uses the polymkeric substance by the acid number with 50mg～120mgKOH/g to constitute.If less than the acid number of 50mgKOH/g, then can cause the reduction of dispersing of pigments stability, if surpass the acid number of 120mgKOH/g, then the color emissivity in the common paper will reduce.
In addition, for example in the invention of (VII), the polymkeric substance preferable weight-average molecular weight that constitutes resin particle contained in the described resin emulsion is 20000～200000.When weight-average molecular weight less than 20000 the time, then, when surpassing 200000, then there is viscosity to uprise as ink for ink-jet print as prolonged preservation stability, thermostability and the stationarity variation of ink for ink-jet print, the tendency of dispersion stabilization variation, the tendency that also has ejection stability to reduce in addition.
In addition, for example in the ink for inkjet recording of the invention of (VII), constituent for the polymkeric substance that constitutes resin particle contained in the resin emulsion, at least in described resin emulsion in contained whole polymkeric substance, with weight convert preferably contain more than 50% with colo(u)rant dispersion in the identical composition of constituent of used polymkeric substance.By using the polymkeric substance of 50% above identical component, just can improve color emissivity and glossiness effectively with less amount, particularly can increase substantially the color emissivity of common paper.
In addition, in the ink for inkjet recording of the invention of (VII), the preferred 20～150nm of the median size of contained resin particle in the resin emulsion.Because when median size is too small, then be difficult to obtain the raising effect of color emissivity or glossiness, when excessive, then have the tendency that color emissivity in the common paper or the glossiness on the glossy paper reduce, so be preferably in the described scope and use.
In addition, in the ink for inkjet recording of the invention of (VII), resin particle contained in the resin emulsion preferably contains with the scope of 0.1～10 weight % with respect to the ink total amount.Because under very few situation, be difficult to obtain the effect of color emissivity or glossiness raising, under too much situation, the tendency that just has color emissivity in the common paper or the glossiness on the glossy paper to reduce, and the tendency that has color emissivity in the common paper or the glossiness on the glossy paper to reduce, therefore be preferably in the described scope and use.
(pigment)
Pigment used among the present invention is for example as black ink usefulness, can enumerate carbon black (C.I. Pigment black 7) classes such as furnace black, dim, acetylene black, channel black; Or metal species such as copper oxide, ferriferous oxide (C.I Pigment black 11), titanium oxide; Nigrosine pigment dyestuffs such as (C.I. Pigment blacks 1), however lower and in water, be difficult to settled carbon black as ink-jet with preferred specific gravity.In addition, as color inks usefulness, can use C.I. Pigment Yellow 73 1 (fast yellow G), 3,12 (the yellow AAA of two diazonium), 13,14,17,24,34,35,37,42 (Zh 1s), 53,55,74,81,83 (the yellow HR of two diazonium), 93,94,95,97,98,100,101,104,108,109,110,117,120,128,138,153,180, C.I. Pigment red 1,2,3,5,17,22 (bright fast scarlets), 23,31,38,48:2 (permanent bordeaux 2B (Ba)), 48:2 (permanent bordeaux 2B (Ca)), 48:3 (permanent bordeaux 2B (Sr)), 48:4 (permanent bordeaux 2B (Mn)), 49:1,52:2,53:1,57:1 (brilliant carmine 6B), 60:1,63:1,63:2,64:1,81 (rhodamine 6G colour lakes), 83,88,101 (red iron oxides), 104,105,106,108 (cadmium reds), 112,114,122 (quinoline a word used for translation ketone magentas), 123,146,149,166,168,170,172,177,178,179,185,190,193,202,209,219,254, C.I. pigment violet 19,23, C.I. pigment blue 1,2,15 (phthalocyanine blue R), 15:1,15:2,15:3 (phthalocyanine blue G), 15:4,15:6 (phthalocyanine blue E), 16,17:1,56,60,63, C.I. Pigment green 1,4,7,8,10,17,18,36 etc.
Preferred 0.5～30% among the present invention as the addition of pigment, yet more preferably 1.0～12%.If the addition below it, then can't guarantee gradation of drop-out colour, if the addition more than it then can produce the viscosity increase of ink or produce structure viscosity in viscosity characteristics, the ejection stability of the ink from ink gun has the tendency of variation in addition.
For example contain C.I. black 7 at the ink of the present invention that uses described pigment to make, C.I. pigment Blue 15: 1, C.I. pigment Blue 15: 2, C.I. pigment Blue 15: 3, C.I. pigment Blue 15: 4, C.I. pigment Blue 15: 6, C.I. pigment green 36, C.I. pigment red 122, C.I. Pigment red 177, C.I. Pigment red 254, C.I. pigment violet 19, C.I. under the situation of the pigment beyond yellow such as pigment Violet 23, from storage stability and ejection excellent in stability are provided, the viewpoint that has the ink for inkjet recording of high Chromaticity in common paper or the glossy paper and the high-luster in the glossy paper concurrently considers that preferably using median size is that 20～100nm and the polymkeric substance with the acid number below the above 80mgKOH/g of 50mgKOH/g disperse.When median size surpassed 100nm, then the gloss on the glossy paper will reduce.Preferred median size is 20～90nm.In addition, if less than the acid number of 50mgKOH/g, then disperse to become unstable.In addition, if surpass the acid number of 80mgKOH/g, then the color emissivity in the common paper will reduce.Preferred acid number is 50mgKOH/g～70mgKOH/g.
In addition, the ink of the present invention that uses described pigment to make is for example containing C.I. Pigment Yellow 73 55, C.I. Pigment Yellow 73 74, C.I. Pigment Yellow 73 79, C.I. Pigment Yellow 73 93, C.I. Pigment Yellow 73 110, C.I. pigment Yellow 12 0, C.I. pigment Yellow 12 8, C.I. pigment yellow 13 8C, C.I. pigment yellow 13 9, C.I. Pigment Yellow 73 150, C.I. Pigment Yellow 73 151, C.I. Pigment Yellow 73 155, C.I. Pigment Yellow 73 156, C.I. under the situation of the such yellow ultramarine of pigment yellow 17 5 and C.I. Pigment Yellow 73 180, from storage stability and ejection excellent in stability are provided, the viewpoint that has the ink for inkjet recording of high Chromaticity in common paper or the glossy paper and the high-luster in the glossy paper concurrently considers, preferably use median size below the above 110nm of 90nm and the polymkeric substance with the acid number below the above 120mgKOH/g of 50mgKOH/g disperse.If median size is less than 90nm, then photostabilization will worsen, and when surpassing 110nm, then the color emissivity on the common paper will reduce.In addition, if less than the acid number of 50mgKOH/g, then disperse to become unstable, if surpass the acid number of 120mgKOH/g, then the color emissivity on the common paper will reduce.
Among the present invention, for example as the ink for inkjet recording of (III), can use C.I. Pigment Yellow 73 1 (fast yellow G), 3,12 (the yellow AAA of two diazonium), 13,14,17,24,34,35,37,42 (Zh 1s), 53,55,74,81,83 (the yellow HR of two diazonium), 93,94,95,97,98,100,101,104,108,109,110,117,120,128,138,153,180, C.I. Pigment red 1,2,3,5,17,22 (bright fast scarlets), 23,31,38,48:2 (permanent bordeaux 2B (Ba)), 48:2 (permanent bordeaux 2B (Ca)), 48:3 (permanent bordeaux 2B (Sr)), 48:4 (permanent bordeaux 2B (Mn)), 49:1,52:2,53:1,57:1 (brilliant carmine 6B), 60:1,63:1,63:2,64:1,81 (rhodamine 6B colour lakes), 83,88,101 (red iron oxides), 104,105,106,108 (cadmium reds), 112,114,122 (quinoline a word used for translation ketone magentas), 123,146,149,166,168,170,172,177,178,179,185,190,193,202,209,219,254, C.I. pigment violet 19,23, C.I. pigment blue 1,2,15 (phthalocyanine blue R), 15:1,15:2,15:3 (phthalocyanine blue G), 15:4,15:6 (phthalocyanine blue E), 16,17:1,56,60,63, C.I. Pigment green 1,4,7,8,10,17,18,36 etc., particularly for yellow ultramarine, because by using PY74, in photostabilization, anti-gaseousness, the high Chromaticity aspect is good, and is therefore preferred.In addition, for magenta pigment, owing to, then be not only high Chromaticity, and can suppress light source dependency (metamerism: metamerism) by using PV19, PR122, PR177 or PR254 or their mixture, therefore preferred, in addition, for green pigment, because by using PB15:1, can improve the bronze phenomenon on the recording surface, therefore preferred.So,, just can realize the raising of comprehensive printing quality by these pigment colour materials are used as the ink group.And, though the text on common paper with also can carrying out in the single color printing and with the record of coloured pigment, yet also can use black pigment.For example as black ink usefulness, can enumerate carbon black (C.I. Pigment black 7) classes such as furnace black, dim, acetylene black, channel black; Or metal species such as copper oxide, ferriferous oxide (C.I Pigment black 11), titanium oxide; Nigrosine pigment dyestuffs such as (C.I. Pigment blacks 1), however lower and in water, be difficult to settled carbon black as ink-jet with preferred specific gravity.
In addition, for example in the ink for inkjet recording of (III), if consider glossiness as described above, then below the preferred 100nm of particle diameter.On the other hand, when the median size that pigment particles is made as less than 20nm, then because photostabilization reduces, and the color development of record thing worsens and becomes obviously, and the color emissivity on the common paper reduces, so more than the preferred 20nm of median size.
In addition, for example the ink for inkjet recording at (III) contains as pigment under the situation of yellow ultramarines such as C.I. Pigment Yellow 73 55,74,79,93,109,110,120,128,138,139,150,151,155,156,175,180, below the above 110nm of the preferred 90nm of dispersing of pigments particle diameter.
In addition, for example the ink for inkjet recording of (III) is by using below the above 110nm of median size 90nm, and the polymkeric substance with the following acid number of the above 120mgKOH/g of 50mgKOH/g disperses, then from storage stability and ejection excellent in stability can be provided, the viewpoint that has the ink for inkjet recording of high Chromaticity in common paper or the glossy paper and the high-luster in the glossy paper concurrently considers it is ideal.If median size is less than 90nm, then photostabilization worsens, and when surpassing 110nm, then the color emissivity on the common paper reduces, and the median size that is provided at all good quality of any aspect of photostabilization common paper color emissivity is restricted to below the above 110nm of 90nm.In addition, if less than the acid number of 50mgKOH/g, then disperse just to become unstable, if surpass the acid number of 120mgKOH/g, then the color emissivity on the common paper will reduce.
In addition, the one-level particle diameter of the described pigment of ink for inkjet recording (III) is preferably, and yellow ultramarine is below the above 80nm of 30nm, and magenta pigment is below the above 70nm of 20nm, and green pigment is below the above 70nm of 20nm.This be because, be in the described scope by the one-level particle diameter that makes each coloured pigment, described dispersion particle diameter will be in its suitable scope.In addition, for example the dispersion particle diameter of the best yellow ultramarine of composition for ink of (III) is below the above 110nm of 90nm, and the one-level particle diameter is below the above 80nm of 30nm.In addition, in the composition for ink (III), below the above 100nm of the preferred 20nm of dispersion particle diameter of magenta pigment, and the one-level particle diameter is below the above 70nm of 20nm.And then below the above 100nm of the preferred 20nm of dispersion particle diameter of composition for ink (III), and the one-level particle diameter is below the above 70nm of 20nm.
In addition, among the present invention, for example at (VI), (VII), (VIII), (X), (XI) and (XV) used pigment is C.I. black 7 in ink-vapor recording thing or the pigment dispersion, C.I. pigment Blue 15: 1, C.I. pigment Blue 15: 2, C.I. pigment Blue 15: 3, C.I. pigment Blue 15: 4, C.I. pigment Blue 15: 6, C.I. pigment green 36, C.I. pigment red 122, C.I. Pigment red 177, C.I. Pigment red 254, C.I. pigment violet 19, C.I. under the situation of the pigment beyond yellow such as pigment Violet 23, from storage stability and ejection excellent in stability are provided, have high Chromaticity in common paper or the glossy paper and the high-luster in the glossy paper concurrently, the viewpoint of fixed ink for inkjet recording considers, preferably use median size below the 90nm and the polymkeric substance with the acid number below the above 80mgKOH/g of 50mgKOH/g come dispersed color.When the median size of polymkeric substance surpassed 90nm, then the gloss on the glossy paper will reduce.In addition, if the acid number of polymkeric substance less than 50mgKOH/g, then disperses just to become unstable.In addition, if the acid number of polymkeric substance surpasses 80mgKOH/g, then the color emissivity in the common paper will reduce.Preferred acid number is 50mgKOH/g～70mgKOH/g.In addition, at (VI), (VII), (VIII), (X), (XI) and (XV) used pigment for example is C.I. Pigment Yellow 73 55 in ink for inkjet recording or the pigment dispersion, C.I. Pigment Yellow 73 74, C.I. Pigment Yellow 73 79, C.I. Pigment Yellow 73 93, C.I. Pigment Yellow 73 110, C.I. pigment Yellow 12 0, C.I. pigment Yellow 12 8, C.I. pigment yellow 13 8C, C.I. pigment yellow 13 9, C.I. Pigment Yellow 73 150, C.I. Pigment Yellow 73 151, C.I. Pigment Yellow 73 155, C.I. Pigment Yellow 73 156, C.I. under the situation of the such yellow ultramarine of pigment yellow 17 5 and C.I. Pigment Yellow 73 180, from storage stability and ejection excellent in stability are provided, have high Chromaticity in common paper or the glossy paper and the high-luster in the glossy paper concurrently, the viewpoint of fixed ink for inkjet recording considers, preferably use median size below the above 110nm of 20nm and the polymkeric substance with the acid number below the above 120mgKOH/g of 50mgKOH/g come dispersed color.If median size is less than 20nm, then photostabilization will worsen, and when surpassing 110nm, then the color emissivity on the common paper will reduce.In addition, if less than the acid number of 50mgKOH/g, then disperse to become unstable, if surpass the acid number of 120mgKOH/g, then the color emissivity on the common paper will reduce.
Among the present invention, for example used yellow ultramarine is considered from sunproof viewpoint in the invention of (XII), as main formation look material, preferably uses C.I. pigment yellow 13 8 at least.By C.I. pigment yellow 13 8 and described combination of polymers are used, just can to obtain in common paper, glossy paper all be high Chromaticity, demonstration high-luster and the also good record thing of photostabilization on glossy paper.In the invention of (XII), except above viewpoint,, preferably also use C.I. Pigment Yellow 73 74 for purposes such as tonings.With C.I. pigment yellow 13 8 and C.I. Pigment Yellow 73 74, just can obtain the effect of the color emissivity raising of common paper by also.In the invention of (XII), also to use under the situation of C.I. pigment yellow 13 8 and C.I. Pigment Yellow 73 74, it contains ratio with preferred 20: 1～1: 10 scope of weight conversion expression.In containing of C.I. Pigment Yellow 73 74, then can't obtain the additive effect of C.I. Pigment Yellow 73 74 than under less than 20: 1 situation.On the other hand, because when more than 1: 10, then the photostabilization ability reduces, therefore preferably in 20: 1～1: 10 scope, use.(XII), preferred 0.5～30% in the invention as the addition of pigment, yet more preferably 1.0～12%.If the addition below it, then can't guarantee gradation of drop-out colour, if the addition more than it then can produce the viscosity increase of ink or produce structure viscosity in viscosity characteristics, the ejection stability of the ink from ink gun has the tendency of variation in addition.In the invention of (XII), described yellow ultramarine is from providing storage stability and ejection excellent in stability, the viewpoint that has the ink for inkjet recording of high Chromaticity in common paper or the glossy paper and the high-luster in the glossy paper concurrently is considered, preferred to use median size be 20～110nm, and the polymkeric substance with acid number of 50～120mgKOH/g disperses.If median size is less than 20nm, then photostabilization will worsen, and when surpassing 110nm, then the color emissivity on the common paper will reduce.In addition, if less than the acid number of 50mgKOH/g, then disperse to become unstable, if surpass the acid number of 120mgKOH/g, then the color emissivity on the common paper will reduce.
(alkylene oxide of glycols (alkylene oxide) affixture etc.)
Ink of the present invention can contain and is selected from 2,4,7,9-tetramethyl--5-decine-4,7-glycol, 3,6-dimethyl-4-octyne-3,6-glycol, 2,4,7,9-tetramethyl--5-decine-4, the alkylene oxide affixture and 3 of 7-glycol, 6-dimethyl-4-octyne-3, more than one in the alkylene oxide affixture of 6-glycol are below the above 1 weight % of the preferred 0.05 weight % of their addition.If less than 0.05 weight %, then the profit of the leakage in the common paper becomes many, not ideal enough.In addition, when surpassing 1 weight %, then, be difficult to prolonged preservation as the storage stability variation of ink for ink-jet print.More preferably below the above 0.7 weight % of 0.1 weight %.
2,4,7,9-tetramethyl--5-decine-4,7-glycol, 3,6-dimethyl-4-octyne-3,6-glycol, 2,4,7,9-tetramethyl--5-decine-4, the alkylene oxide affixture market of 7-glycol is on sale, and Surfynol 104, Surfynol82, Surfynol 2502, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, the river that can be used as day letter KCC system ground the acetylenol EOO of fine chemistry industry Co., Ltd. system, acetylenol E40, acetylenolE100 etc. and obtained.
(1, the 2-alkylene glycol)
Ink of the present invention preferably contains 1, the 2-alkylene glycol.1, preferred especially 1 in the 2-alkylene glycol, 2-hexylene glycol and/or 4-methyl isophthalic acid, the 2-pentanediol, by using them, the ejection stability of ink for ink-jet print will improve, and the leakage profit on common paper during printing reduces.
In addition, among the present invention, for example as the ink for inkjet recording of (VIII), can and with the C of 0.5～15 weight % 4～C 101,2-alkylene glycol, 5～30 weight % remove with described corresponding 1 other C outside the 2-alkylene glycol 10Following polyalcohols.In the invention of (VIII), C 4～C 101, the ejection of 2-alkylene glycol during for the ejection of the high-speed and continuous of ink droplet plays a role, and is that 0.5～15 weight % just can guarantee stable ejection by making content.When being less than 0.5 weight %, then the weight of ink droplet becomes too much easily in high-speed and continuous ejection, thereby the bad ejection instability of the providing ink that causes being accompanied by showerhead is arranged or cause leaking the situation of profit in field printing (solid printing).Under situation more than 15 weight %, can cause weight by the ink droplet too small ejection instability that causes that becomes, and field printing (solid printing) can not tamp (generation white line), can't obtain enough color emissivities etc., becomes the reason that causes that printing quality reduces.As the C that in the ink of (VIII), uses 4～C 101, the 2-alkylene glycol, specifically, can enumerate 1,2-propylene glycol, 1,2-butyleneglycol, 1,2-pentanediol, 1,2-hexylene glycol, 1,2-heptanediol, 1,2-ethohexadiol, 1,2-decanediol, 3,3-dimethyl-1,2-butyleneglycol, 4-methyl isophthalic acid, 2-pentanediol etc., more preferably 1,2-hexylene glycol and 4-methyl isophthalic acid, the 2-pentanediol.Using pigment of the present invention, also used under their situation effect of the leakage profit in the time of just can obtaining to improve the ejection stability of ink and reduce plain paper.
In addition, in the ink of (VIII), remove described 1, the C beyond the 2-alkylene glycol 10Following polyalcohols plays a role to the common ejection of low speed in the comparison, the ejection of the ink droplet at intermittence, by being made as 5～30 weight %, just can realize stable ejection.Under the very few situation of content, ink is dry easily, if do not apply in the short period of time at the utmost point, then ink will solidify at spray nozzle part, becomes the reason that causes that ejection is bad.In addition, under too much situation,, rise, cause that flight is crooked, cause spraying bad because of the evaporation of slight moisture can make viscosity though can not cause the curing of ink.Discoveries such as the inventor, this phenomenon are with described 1, and the situation that the 2-alkylene glycol is used in combination becomes obviously, remove described 1, the C beyond the 2-alkylene glycol 10The content of following polyalcohols is in the scope of 5～30 weight %, can guarantee good ejection stability.
Usedly in the ink as (VIII) remove 1, the C beyond the 2-alkylene glycol 10Following polyalcohols, can enumerate glycol ether, triglycol, Tetraglycol 99,1-butoxy oxyethyl group propyl alcohol, dipropylene glycol, three tripropylene glycol, 1 that contracts specifically, ammediol, 1,3-butyleneglycol, 1,5-pentanediol, hexylene glycol, ethohexadiol, glycerine, trimethylolethane, TriMethylolPropane(TMP) etc., more preferably triglycol, dipropylene glycol, 1, ammediol, glycerine, TriMethylolPropane(TMP).In addition, in (VIII) ink, C 4～C 101, the 2-alkylene glycol with remove described 1, the C beyond the 2-alkylene glycol 10The scope content of following polyalcohols and that preferably be in 6～40 weight %.Owing to temporarily do not using under the situation of ink-jet printer, when being less than 6 weight %, then the moisture evaporation of ink will advance, cause the obstruction of the spray nozzle part that causes by drying easily, when more than 40 weight %, then cause the ejection instability that rises and cause by the viscosity of ink easily, therefore preferably be in described scope.In addition, described 1,2-alkylene glycol and polyalcohols contain the scope that ratio preferably is in 1: 50～1: 1.5.Because when the ratio of polyalcohols is higher than 1: 50, then can't obtain fully as 1, ejection stability when the high-speed and continuous of the additive effect of 2-alkylene glycol sprays, in addition, when being lower than 1: 1.5, the then dry aggravation easily of ink impacts intermittently spraying or stopping up Restoration, therefore preferably is in described scope.The ink for inkjet recording of invention (VIII) is as other mode, also preferably contain 0.5～15 weight % with R 1O-(C mH2 mO) n-R 2(m and n are the integer more than 1, m * n≤10, R 1And R 2Be C 8Following alkyl, R 1And R 2Both can be the same or different) expression gylcol ether.As mentioned above, about containing 1, the ink of 2-alkylene glycol and gylcol ether, open in the 2005-154548 communique the spy, provide by also making up and reduced the method that realizes duplex printing to the leakage profit of common paper with nonionic surfactant, yet in the document, there is not record about the problem of addition and ejection stability, in fact, according to the addition difference, have the situation that causes spraying the stability reduction.That is, in the ink for inkjet recording of the invention of (VIII), by with described 1, the addition of 2-alkylene glycol is made as previously mentioned, and the addition of described gylcol ether is made as 0.5～15 weight %, just can guarantee the stable ink ejection.Described gylcol ether plays a role for the ink ejection stability of the common ejection of low speed in the comparison, because under very few situation, usually the ink weight of ejection is unstable and the tendency of easy fluctuation arranged, in addition under too much situation, just have Lou profit or ooze out the influence that waits printing quality, so preferably in described scope, use.
And, used gylcol ether in the ink for inkjet recording for (VIII), as preferred example, can enumerate and be selected from two (three) ethylene glycol monobutyl ethers, (two) propylene glycol monobutyl ether, two (three) glycol monomethyl amyl ethers and two (three) ethylene glycol ethers more than one.For example pass through pigment used in the ink for inkjet recording of (VIII) and their combinations, except can improving ejection stability, the effect of the leakage profit in the time of can also obtaining to reduce plain paper, printing quality improves.In addition, as more preferred example, can enumerate and be selected from two (three) ethylene glycol monobutyl ethers and (two) propylene glycol monobutyl ether more than one.
In addition, in the ink for inkjet recording of the invention of (VIII), C 4～C 101,2-alkylene glycol and described gylcol ether contain the scope that ratio preferably is in 10: 1～1: 10.Described 1, containing under the too much situation of ratio of 2-alkylene glycol, then can't obtain fully by adding the described effect that gylcol ether obtains, it is opposite when gylcol ether is too much, then can't pass fully and contain 1,2-alkylene glycol and the effect that obtains, therefore containing ratio preferably is made as described scope.In addition, in the ink for inkjet recording of the invention of (VIII), C 4～C 101, the 2-alkylene glycol, remove described 1, the C beyond the 2-alkylene glycol 10Following polyalcohols, with R 1O-(C mH 2mO) n-R 2(m and n are the integer more than 1, m * n≤10, R 1And R 2Be C 8Following alkyl, R 1And R 2Both can be the same or different) content of the gylcol ether of expression and preferably be in the scope of 7～40 weight %.Temporarily do not using under the situation of ink-jet printer, because when being less than 7 weight %, then the moisture evaporation of ink will advance, cause the obstruction of the spray nozzle part that causes by drying easily, when more than 40 weight %, then cause the ejection instability that rises and cause by the viscosity of ink easily, therefore preferably be in described scope.
(butyl ethers)
In addition, preferably contain and be selected from two (three) ethylene glycol monobutyl ethers, (two) propylene glycol monobutyl ether, two (three) glycol monomethyl amyl ethers and two (three) ethylene glycol ethers more than one.By using these gylcol ethers, in ink-jetting style, just can further reduce the leakage profit when on common paper, printing, print quality improves.
(propylene glycol)
In addition, ink of the present invention preferably contains 2-butyl-2-ethyl-1, ammediol, and by also using 2-butyl-2-ethyl-1, ammediol, the glossiness on the glossy paper will improve, and the color emissivity on the common paper will improve.Preferred addition is 0.1 weight %～10 weight %.
Among the present invention,, preferably contain the following 2-butyl-2-ethyl-1 of the above 10 weight % of 0.1 weight %, ammediol for example as the ink for inkjet recording of (V).By contain this additive in ink system, just can improve color emissivity on the common paper and the glossiness on the glossy paper.Even this additive is a small amount of, does not compare the effect of improving that yet can see printing quality with there being the ink that adds, yet preferably add more than the 0.1 weight %, more than the preferred 0.5 weight %.On the other hand, because the solvability in this additive hydrotropisms ink is low, the interpolation that surpasses 10 weight % can't be dissolved in the ink, causes to be separated, and is therefore not ideal enough.Consider that from the viewpoint of the storage stability of ink preferred addition is below 5.0 weight %, more preferably below the 2.0 weight %.
(TriMethylolPropane(TMP))
In addition, among the present invention,, can contain the following TriMethylolPropane(TMP) of the above 20 weight % of 1 weight % for example as (III), (IV) and ink for inkjet recording (V).By contain this additive in ink system, can obtain following effect, that is, improve the obstruction Restoration of shower nozzle, and can suppress the accumulation that the drying that is accompanied by the throwing ink distribution water in ink-jet recording device in boundless when printing produces.Even this additive is on a small quantity, compare also with the ink that does not have interpolation and can see described effect, yet owing to when less than 1 weight %, be difficult to obtain tangible improvement, therefore more than the preferred 1 weight %.On the other hand, surpass the interpolation of 20 weight % because improvement of stopping up and accumulation suppress effect to the end, therefore not ideal enough.Consider that from the viewpoint of the storage stability of ink preferred addition is below 15 weight %, more preferably below the 10 weight %.
In addition, among the present invention, for example as the ink for inkjet recording of (VIII), in order to be difficult to cause the obstruction of ink gun, except removing C 4～C 101, the C of 2-alkylene glycol 10Beyond the following polyalcohols, also can contain and be selected from tetrose, pentasaccharides and six sugar more than one.
In addition, among the present invention,,, also can contain and be selected from glycerine, trimethylolethane, TriMethylolPropane(TMP), tetrose, pentasaccharides and six sugar more than one in order to be difficult to cause the obstruction of ink gun for example as the ink for inkjet recording of (XII).
In addition, polymkeric substance of the present invention has carboxyl, yet as its counter ion, preferably contains trolamine and/or tripropanol amine.By using trolamine and/or tripropanol amine,, also be difficult to cause the obstruction of ink for ink-jet print even under drying regime.
And, among the present invention, as required, also can also use dispersion agent, surface tension adjustment agent or permeate agent (tensio-active agent), moistening drying to prevent that agent, sanitas, sterilant, pH from adjusting agent, rust-preventive agent, wetting Agent for Printing Inks and other additive.They both can use separately, also can be also with two or more.
(manufacture method of ink for inkjet recording)
Manufacture method as ink for inkjet recording of the present invention, for example can enumerate following method etc., promptly, utilize high-speed stirring to come emulsification with alkali such as polymkeric substance, aqueous medium, sodium hydroxide ink for ink-jet print of the present invention, then drop into pigment etc., disperse powerfully with decollator (disper) etc.In addition, also can implement following method etc., that is, as required, disperse with three roller runner millings etc., to the pigment syrup of gained with high pressure dispersion machine etc. with colo(u)rant dispersion to stipulating particle diameter, from the dispersible pigment dispersion of gained, remove organic solvent etc. then.
As described high pressure dispersion machine, be not particularly limited, can enumerate miniature fluidizer (Microfluidics company), Ultimizer (Sugino Machine company), wet shotcrete technology pulverizer (Genus company), nanometer machine (Nanomizer company) etc.
As long as the pressure when disperseing with described high pressure dispersion machine can reach required pigment particle size, no matter be what can, yet preferred 100MPa～300MPa.If less than 100MPa, then disperse particle diameter to become big easily, the expensive time when disperseing, if greatly do not increase the wheel number of times, then be difficult to become stable dispersion, economical inadequately.And, can't reach under the situation of required pigment particle size, also can in the scope of described pressure, increase and disperse number of times, or pressurize and disperseing.
In addition, in the manufacture method of ink for ink-jet print of the present invention, also can use the following ink for ink-jet print polymers soln that obtains, promptly, to described ink for ink-jet print that polymerization finishes with polymkeric substance in interpolation alkaline solution and heating, thereafter solvent is removed, with displacements such as ion exchanged waters.
In addition, used the dispersing method of used polymkeric substance among the present invention preferred so that the mode of polymkeric substance coverage pigment Phase inversion emulsification in water.By using phase conversion emulsifying, it is stable that ink will become, and the color emissivity of common paper improves.
In addition, also can use the ink for ink-jet print polymers soln that obtains as followsly, promptly, the described ink for ink-jet print that polymerization is finished utilizes underpressure distillation to remove with polymkeric substance and desolvates, the ink for ink-jet print of gained is pulverized with the solid substance of polymkeric substance, added ion exchanged water, alkaline solution etc. and heating for dissolving.Under this situation, need from the dispersible pigment dispersion of gained, not remove organic solvent etc. thereafter.
As alkali used in the described alkaline solution, can enumerate mineral alkalis such as three grades of alkyl alcohol amines such as trolamine, tripropanol amine, sodium hydroxide, potassium hydroxide, lithium hydroxide etc.
Particularly, in the present invention, for example as the pigment dispersion and the manufacture method thereof of (VI), can use pigment is modified to the phase conversion emulsifying that covers polymkeric substance of the present invention, consider the dispersiveness of this polymkeric substance in addition, the addition optimizing of used dispersion agent during with Phase inversion emulsification according to the weight-average molecular weight of polymkeric substance.That is, under the situation below 120000 more than 50000, remove the dispersion dosage that anhydrates during dispersion with respect to more than the pigment optimization 95 weight % below the 300 weight % in the weight-average molecular weight of polymkeric substance.When being less than 95 weight %, then can't form sufficient dispersion state, when surpassing 300 weight %, then polymkeric substance reduces to the arrival frequency of surface of pigments in addition, the expensive time in Phase inversion emulsification, and polymkeric substance is abundant inadequately to the modification of surface of pigments.
In addition, as the manufacture method of the pigment dispersion of (VI), the weight-average molecular weight of polymkeric substance less than 50000 situation under, disperse dosage with respect to more than the pigment optimization 45 weight % and less than 180 weight %.Owing to, when being less than 45 weight %, then can't form sufficient dispersion state with described identical reason, in addition when 180 weight % are above, then polymkeric substance reduces to the arrival frequency of surface of pigments, the expensive time in Phase inversion emulsification, and polymkeric substance is abundant inadequately to the modification of surface of pigments.In the weight-average molecular weight of described polymkeric substance under the situation below 120000 more than 50000, if remove when disperseing the dispersion dosage that anhydrates with respect to pigment below 300 weight % more than the 95 weight %, then can obtain its effect, yet more preferably below the above 280 weight % of 50 weight %.In addition, if the weight-average molecular weight of this polymkeric substance less than 50000, the dispersion dosage so long as 45 weight % are above less than 180 weight % get final product, however more preferably more than the 50 weight % below the 150 weight %.By use phase conversion emulsifying under this condition, it is stable that ink will become, and the color emissivity of common paper improves.
In addition, among the present invention, as the ink for inkjet recording and the manufacture method thereof of (IX), in the dispersion that makes paints, more than the preferred 150MPa of the processing pressure of high-pressure homogenizer.If less than 150MPa, then will worsen as the storage stability of ink-jet with paint ink.More preferably below the above 245MPa of 180MPa.Below the further preferred above 220MPa of 190MPa.When processing pressure is high, then become excessive dispersion easily, will worsen as the storage stability of ink-jet thus with paint ink.Taking turns number of times preferred 3 in addition takes turns (passes) above 8 and takes turns following.If take turns less than 3, then disperse fully inadequately, will worsen as the storage stability of ink-jet thus with paint ink, the glossiness on the glossy paper also can worsen in addition.When taking turns above 8, then become excessive dispersion easily, will worsen as the storage stability of ink-jet thus with paint ink.
In addition, among the present invention, for example as the ink-jet of (IX) with paint ink and manufacture method thereof, preferably to described pigment and the polymers soln that becomes dispersion agent with high-pressure homogenizer under the processing pressure more than the 150MPa, handle 30 take turns following.In addition, more preferably use and carry out 3 and take turns above 8 and take turns following dispersion treatment and the dispersible pigment dispersion made, modulate ink for inkjet recording by mixing with the vehicles composition.According to this kind manufacture method, the glossiness on the glossy paper will improve.
Ink-jet used dispersion machine in paint ink and the manufacture method thereof as (IX), preferred non-medium dispersing mode wherein can be enumerated wet shotcrete technology pulverizer (Genus company), nanometer machine (Nanomizer company), homogenizer (Gorlin company), Ultimaizer (Sugino Machine company) and miniature fluidizer (Microfluidics company) etc.
In addition,, preferred 0.5～30% in the ink-jet of (IX) as the addition of pigment with in the paint ink, yet more preferably 1.0～15%.If the addition below it, then can't guarantee gradation of drop-out colour, if the addition more than it then can produce the viscosity increase of ink or produce structure viscosity in viscosity characteristics, the ejection stability of the ink from ink gun has the tendency of variation in addition.In addition, as the ink-jet of (IX) vehicles composition, can use tensio-active agent, organic solvent and wetting Agent for Printing Inks etc. with paint ink.Scope below surface tension being made as the above 40mN/m of 20mN/m can directly be widened the point of being printed the ink-jet to the viewpoint of the width of the best and consider, preferably adds tensio-active agent at least.This tensio-active agent more preferably is selected from more than one in acetylene series alcohol surfactants, acetylenic glycol (acetylene glycol) class tensio-active agent and the silicon class tensio-active agent.By using these tensio-active agents, then can reduce the leakage profit on the common paper especially, the point on the dedicated paper directly can be widened width into the best.In addition, for the ink-jet of (IX) is made as the following scope of the above 40mN/m of 20mN/m with the surface tension of paint ink, preferably add alkylene glycol monoalky lether and/or 1 at least, the 2-alkylene glycol.This alkylene glycol monoalky lether preferred repeat units is the alkylene glycol below 10, and the alkyl oxide of preferred carbon number 4～10.In addition, preferred two (three) ethylene glycol monobutyl ethers of described alkylene glycol monoalky lether and/or (two) propylene glycol monobutyl ether.In addition, described 1, the 2-alkylene glycol is preferred 1,2-hexylene glycol and/or 1,2-heptanediol.Owing to utilize their interpolation, the drying property of printing improves, even printing continuously, the printing portion of front also can not be transferred to the back side of medium thereafter, therefore can realize flying print.It is described that to be selected from more than one the addition of material in acetylenic glycol class tensio-active agent, acetylene series alcohol surfactants and the silicon class tensio-active agent preferred more than 0.1% below 5%.In this kind ink for inkjet recording, preferably contain at least described be selected from acetylenic glycol class tensio-active agent, acetylene series alcohol surfactants and the silicon class tensio-active agent more than one and be selected from two (three) ethylene glycol monobutyl ethers, (two) propylene glycol monobutyl ether and 1, more than one in the 2-alkylene glycol.The described addition preferred 0.01%～0.5% that is selected from more than one materials in acetylenic glycol class tensio-active agent, acetylene series alcohol surfactants and the silicon class tensio-active agent, be selected from two (three) ethylene glycol monobutyl ethers, (two) propylene glycol monobutyl ether and 1, the addition of more than one in the 2-alkylene glycol is preferred more than 1%.
In addition, among the present invention, for example, preferably used the pigment dispersion of used polymkeric substance among the present invention in the finishing of self-dispersion type pigment particles as the ink for inkjet recording of (X).This kind pigment dispersion can obtain by using the phase conversion emulsifying of modifying self-dispersion type pigment particles surface in the mode of overlie polymer to wait.By operation like this, it is stable that ink will become, and the color emissivity of common paper improves.
In addition, among the present invention, for example in the manufacturing of the pigment dispersion of the ink for inkjet recording of (X), can't reach under the situation of required pigment particle size, though also can in described pressure range, increase the dispersion number of times, or pressurize disperses, yet considers from the viewpoint of economy, is preferably in when disperseing number of times to be at most below 30 times and can obtains required dispersing morphology.
In addition, as used high pressure dispersion machine in the manufacturing of (XIV) and ink for inkjet recording (XVI), though be not particularly limited, but from pollutent sneak into or the viewpoint of dispersion stabilization is considered, the preferred dispersion machine that uses no medium can be enumerated miniature fluidizer (Microfluidics company), Ultimizer (Sugino Machine company), wet shotcrete technology pulverizer (Genus company), nanometer machine (Nanomizer company) etc. as its example.
In addition, among the present invention, for example as the ink for inkjet recording of (XV) with pigment dispersion and manufacture method thereof, ink for inkjet recording, the preferred phase conversion emulsifying that uses polymkeric substance that the pigment mulched ground is modified, like this, it is stable that ink will become, and the color emissivity of common paper improves.Ink-vapor recording at (XV) is used in the manufacturing of pigment dispersion, preferably utilizes the not processing of the high-pressure homogenizer enforcement of working medium.If the dispersion of working mediums such as ball mill is then because the easy broadening of size-grade distribution causes the pollution of medium easily, therefore not ideal enough.As high-pressure homogenizer, can enumerate miniature fluidizer (Microfluidics company), Ultimizer (Sugino Machine company), wet shotcrete technology pulverizer (Genus company), nanometer machine (Nanomizer company) etc.
In addition, among the present invention, for example the wet cake of the pigment in the manufacture method of the ink for inkjet recording of (XIII) can be made as followsly.That is, after having synthesized pigment, make crude product, by using this rough to carry out salt assistant research fellow mill with the pigment miniaturization.Thereafter the desalting treatment of utilizing ion exchanged water to clean, making contains the wet cake of the state of water.Under the situation of the pigment that uses powder, the pigment water is got wet, forcibly disperse and the wet paint that obtains uses as runner millings such as using edge-runner mill or three roller runner millings.
Used dispersion machine in the manufacturing process as the pigment dispersion in the manufacture method of this kind (XIII), preferred non-medium dispersing mode wherein can be enumerated wet shotcrete technology pulverizer (Genus company), nanometer machine (Nanomizer company), homogenizer (Gorlin company), Ultimaizer (SuginoMachine company) and miniature fluidizer (Microfluidics company) etc.By making described ink for inkjet recording like this, just can form following ink-jet paint ink, that is, in common paper, be high Chromaticity, on dedicated paper, have high-luster, the ejection excellent in stability of the ink from ink gun.
And, in the manufacturing process of pigment dispersion (XIII) more than the preferred 150MPa of the processing pressure of used high-pressure homogenizer.If less than 150MPa, then will worsen as the storage stability of ink-jet with paint ink.More preferably below the above 245MPa of 180MPa.Below the further preferred above 220MPa of 190MPa.When processing pressure is high, then become excessive dispersion easily, will worsen as the storage stability of ink-jet thus with paint ink.Take turns in addition number of times preferred 3 take turns above 8 take turns following.If take turns less than 3, then disperse fully inadequately, will worsen as the storage stability of ink-jet thus with paint ink, the glossiness on the glossy paper also can worsen in addition.When taking turns above 8, then become excessive dispersion easily, will worsen as the storage stability of ink-jet thus with paint ink.
In addition, the ink-jet of invention (XIII) is with in the manufacture method of paint ink, use behind the synthetic dyestuff without the wet cake of this pigment of drying process, or use pigment with powder shaped to mix with water and with edge-runner mill or the dispersion of three roller runner millings and must this hybrid pigment.Because they are not dry status, therefore it can be disperseed equably.In addition, preferably mix with polymers soln that becomes dispersion agent and dispersion medium, with the pigment of described wet condition with become the polymers soln and dispersant of dispersion agent after, in high-pressure homogenizer, carry out dispersion treatment, make by mixing with the vehicles composition.Dispersion will become evenly like this, and the glossiness on the glossy paper will improve.When will be by temporary transient drying treatment pigment powder when directly using, then because cohesion again, therefore be difficult to obtain have the dispersion of the size-grade distribution of homogeneous.Used the ink-jet of inhomogenous dispersion also to worsen easily with the glossiness of paint ink on glossy paper.
And, in the manufacture method of (XIII), be under the situation of pigment dyestuff at pigment, utilize salt milling etc. can realize miniaturization, the glossiness on the glossy paper is improved.
(ink jet recording method)
Ink jet recording method of the present invention is that the known in the past ink jet recording method of the drop utilization of the ink for inkjet recording of variety of way of the present invention is supplied with to recording mediums such as paper, forms the method for image.
Particularly, in the present invention, for example as the ink jet recording method of the invention of (XI), can utilize by use making such as aforesaid polymkeric substance, composition, method, be at least cyan, magenta, xanchromatic ink for inkjet recording, this ink is applied in proper order with cyan, magenta, xanchromatic, and formation comprises the tertiary colo(u)r(s) of black and realizes image.
In the ink jet recording method of (XI), preferably from beginning most that printed medium is applied corresponding cyan.By at first applying corresponding cyan, in with the repeatedly look of cyan as integrant, just can obtain the highest color emissivity, on the other hand, when applying other ink before applying cyan, then because of the influence of the previous point that applies, the color emissivity of cyan will reduce, and profit takes place to leak easily, therefore preferably at first apply cyan.
In addition, in the ink jet recording method of (XI), be preferably at last recording medium is applied corresponding yellow ink.By the yellow ink that in the end applies, in with the repeatedly look of yellow ink as integrant, just can make the glossiness on the glossy paper the highest, on the other hand, because when applying other ink after yellow ink, then except the transparency of yellow ink, the transparency of the ink that it is after-applied also can be lost, cause the phenomenon that glossiness reduces, therefore be preferably in and apply yellow ink at last.
In addition, in the ink jet recording method of (XI), preferably the magenta ink with correspondence applies between cyan and yellow ink.Because magenta ink is positioned at the centre of the characteristic of cyan and yellow ink, with the mixing of cyan in can demonstrate and yellow identical effect, with the mixing of yellow ink in, can demonstrate the effect identical with cyan, apply in the middle of therefore being preferably in.
In addition, in the ink jet recording method of (XI), surpass under cyan, magenta, yellow three kinds the situation at the ink kind that constitutes the ink group, preferably the ink near the color of cyan applies with the color sequences between cyan and magenta, applies with the color sequences between magenta and yellow near the xanchromatic ink.By applying, in comprising the repeatedly look of black, just can embody color emissivity and glossiness most effectively with this kind order.
In addition, in the ink jet recording method of (XI), preferably use following ink-jet recording device to print, promptly, the color alignment of the nozzle in the printhead is vertical with the printing scanning direction of shower nozzle, promptly parallel with the scanning direction of recording medium, and be followed successively by cyan, magenta, yellow in proper order to the morning and evening that applies of recording medium.In ink-vapor recording, consider that from the viewpoint of print speed applying on recording medium is preferably in printhead and prints in the scanning, can apply in outlet and loop both sides.In the ink-jet recording device 1 of Fig. 1, the scanning direction (hereinafter referred to as main scanning direction) of arrow 2 expression printheads 3, the scanning direction (hereinafter referred to as sub scanning direction) of arrow 4 expression recording mediums 5, at this moment, the nozzle arrangement of printhead 3 is shown in the printhead 3a of Fig. 2, under the situation that the arrangement and the sub scanning direction 4a of color are arranged in parallel, under any situation of the outlet of main-scanning 2a1, loop 2a2, apply, applying of cyan 6a, magenta 7a, yellow 8a in proper order all can be identical.Like this, just can use outlet, loop both sides to print action, thereby can carry out good printing at high speed.
In addition, in the ink jet recording method of (XI), printing when preferably using following ink-jet recording device only to carry out outlet scanning, that is, the color alignment of printhead is parallel with the printing scanning direction of shower nozzle, promptly, on the scanning direction of printhead, putting in order is cyan, magenta, yellow, perhaps preferably uses to put in order to be the ink-jet recording device of yellow, magenta, cyan to print when only scanning in the loop.Under this situation, because printing scanning becomes outlet or loop certain, therefore print speed is slow for comparing longitudinally with color alignment, yet in the device of extended spread, along with number of color increases, it is big that shower nozzle length 9 becomes pro rata, it is big that printing zone in the scanning once becomes, and therefore just produces the maximization that causes recording unit, the problems such as accuracy at target reduction of point are different with it, has following advantage in the horizontally-arranged row, that is, because shower nozzle length 9 does not change with number of color, therefore the printing zone in the scanning does not once change yet, recording unit also is difficult to cause the reduction of accuracy at target a little in addition so long as get final product laterally slightly becoming big degree.Like this, under the more situation of number of color, as shown in Figure 3, in the horizontally-arranged row, use is arranged the ink-jet recording device that forms with cyan 6b, magenta 7b, yellow 8b, only when outlet scanning (2b), print, in addition, as shown in Figure 4, use with yellow 8c, magenta 7c, cyan 6c and arrange the ink-jet recording device that forms, only when loop scanning (2c), print, by adopting this method, just can obtain in common paper, glossy paper is high Chromaticity all, and has good glossiness on glossy paper, comprises the printed images of the repeatedly look of black.
Embodiment
Below will enumerate embodiment the present invention is further elaborated, yet the present invention is not limited to these embodiment, only otherwise break away from purport of the present invention, can carry out various changes.
[example I]
(example I-1)
The separating flask (separable flask) of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel inner with nitrogen replacement after, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, cyclohexyl acrylate 483.0 weight parts, methacrylic acid 33.3 weight parts, vinylformic acid 25.2 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carry out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtain resin and form admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 43000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes, add Cyanine BlueG-500pure-A (C.I.PB15:1 then with the high speed dispersion device; Adret pigment Co., Ltd. system) 120.0 weight parts stirred 1 hour with the high speed dispersion device, obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtain dispersible pigment dispersion with the pressure of 200MPa.
Then, from dispersible pigment dispersion, utilize and used the underpressure distillation of vaporizer to remove methyl ethyl ketone, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.
Make ink for inkjet that ink Table I-1 shown in form thereafter.
(example I-2)
Except substitutional crylic acid cyclohexyl 483.0 weight parts, and use benzyl acrylate 483.0 weight parts, and methacrylic acid is made as 0 part, vinylformic acid is made as beyond 50.4 weight parts, carry out in the same manner with embodiment 1, make the ink for inkjet of the composition example 2 shown in the Table I-1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 60mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 32000.
(example I-3)
Except t-butylperoxy (2-ethylhexanoate) 4.8 weight parts being made as 7.2 weight parts, carry out in the same manner with embodiment 1, make the ink for inkjet of the composition example 3 shown in the Table I-1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 80mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 80000.
(example I-4)
Except t-butylperoxy (2-ethylhexanoate) 4.8 weight parts being made as 7.2 weight parts, carry out in the same manner with embodiment 2, make the ink for inkjet of the composition example 4 shown in the Table I-1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 55mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 39000.
(example I-5)
Except Cyanine Blue G-500pure-A 480.0 weight parts of replacement pigment concentration 25 weight %, and used Fast Yellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 120.0 weight parts, carries out in the same manner, make the ink for inkjet of the composition example 5 shown in the Table I-1 with embodiment 1.
(example I-6)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used beyond FastYellow 7413-A 120.0 weight parts, carried out in the same manner, made the ink for inkjet of the composition example 6 shown in the Table I-1 with embodiment 4.
(example I-7)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used Pigment Violet GC227-A (C.I.PY19; Adret pigment Co., Ltd. system) beyond 120.0 weight parts, carries out in the same manner, make the ink for inkjet of the composition example 7 shown in the Table I-1 with embodiment 1.
(example I-8)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used beyond Pigment Violet GC227-A 120.0 weight parts, carried out in the same manner, made the ink for inkjet of the composition example 8 shown in the Table I-1 with embodiment 4.
(example I-9)
Except replacing diethylene glycol monomethyl ether 200.0 weight parts, cyclohexyl acrylate 483.0 weight parts, methyl acrylate 66.6 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, and used beyond diethylene glycol monomethyl ether 200.0 weight parts, cyclohexyl acrylate 540.6 weight parts, methyl acrylate 32.4 weight parts, vinylformic acid 27.0 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, carry out in the same manner with embodiment 1, make the ink for inkjet of the composition example 9 shown in the Table I-1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 33000.
(example I-10)
Except replacing diethylene glycol monomethyl ether 200.0 weight parts, cyclohexyl acrylate 483.0 weight parts, methyl acrylate 66.6 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, and diethylene glycol monomethyl ether 200.0 weight parts have been used, cyclohexyl acrylate 363.0 weight parts, methyl acrylate 66.6 weight parts, vinylformic acid 50.4 weight parts, stearyl methacrylate 120.0 weight parts and t-butylperoxy (2-ethylhexanoate) 5.4 weight parts, in addition, not with dropping temperature, keeping temperature and temperature of reaction to be made as under 80 ℃ carries out, but be made as beyond carrying out under 85 ℃, carry out in the same manner with embodiment 1, make the ink for inkjet of the composition example 10 shown in the Table I-1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 130mgKOH/g, and weight-average molecular weight is 33000.
(example I-11)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, temperature sensor, dropping funnel is fully with nitrogen replacement, in separating flask, add methyl ethyl ketone 200.0 weight parts, when stirring, be warmed up to 80 ℃.
Then, in dropping funnel, add methyl ethyl ketone 200.0 weight parts, cyclohexyl acrylate 520.8 weight parts, methacrylic acid 36.6 weight parts, vinylformic acid 30.6 weight parts, methacrylic acid 2-(diethylamino) ethyl ester 12.0 weight parts and 2,2 '-azobis isobutyronitrile, 4.8 weight parts dripped in separating flask with 4 hours down at 80 ℃.
After finishing to drip, after having kept 1 hour with 80 ℃, add 2,2 '-azobis isobutyronitrile, 0.8 weight part carries out reaction in 1 hour again under 80 ℃.
Be through with aging after, be cooled to 20 ℃., add methyl ethyl ketone 200.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution thereafter.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 80mgKOH/g, and weight-average molecular weight is 33000.
Then, in polymer composition solution 120.0 weight parts, add 30% aqueous sodium hydroxide solution, 6.0 weight parts, stirred 5 minutes with the high speed dispersion device, then adding pigment concentration is the Cyanine Blue G-500pure-A480.0 weight part of 25 weight %, stirred 1 hour with the high speed dispersion device, obtain the colo(u)rant dispersion slip.
After this, utilize high-pressure homogenizer (miniature fluidizer) to repeat 20 this colo(u)rant dispersion slip and take turns dispersion, obtain dispersible pigment dispersion with the pressure of 200MPa.
Then, from dispersible pigment dispersion, utilize underpressure distillation to remove methyl ethyl ketone, utilize separating centrifuge (05P-21) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, ink for ink-jet print is adjusted into pigment concentration with pigment dispersion reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.Make ink Table I-1 shown in and form 11 ink for inkjet thereafter.
(example I-12)
Except substituent methyl ethyl ketone 200.0 weight parts, cyclohexyl acrylate 520.8 weight parts, methyl acrylate 36.6 weight parts, vinylformic acid 30.6 weight parts, methacrylic acid 2-(diethylamino) ethyl ester 12.0 weight parts and azobis isobutyronitrile 4.8 weight parts, and methyl ethyl ketone 200.0 weight parts have been used, cyclohexyl acrylate 502.8 weight parts, methyl acrylate 36.6 weight parts, vinylformic acid 30.6 weight parts, beyond methacrylic acid 2-hydroxyl ethyl ester 30.0 weight parts and azobis isobutyronitrile 4.8 weight parts, carry out in the same manner with embodiment 11, make the ink shown in the Table I-1 and form 12 ink for inkjet.
In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 80mgKOH/g, and weight-average molecular weight is 32000.
(example I-13)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, temperature sensor, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.
Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, cyclohexyl acrylate 483.0 weight parts, methyl acrylate 66.6 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down at 80 ℃.
After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carry out reaction in 1 hour again with 80 ℃.
Utilize underpressure distillation remove diethylene glycol monomethyl ether thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% ink for ink-jet print polymer composition solution.Get the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, obtain the solid substance of polymer composition.
Then, in the separating flask of the 2000ml that has possessed whipping appts, return line, temperature sensor, dropping funnel, add solid substance 300.0 weight parts and ion exchanged water 727.0 weight parts of chippy polymer composition, stir.
Then, in dropping funnel, add 30% aqueous sodium hydroxide solution, 173.0 weight parts, dripped in the clockwise separating flask with 5 minutes.
After dripping end, be warmed up to 90 ℃, after having kept 2 hours under 90 ℃, cool to room temperature obtains polymer composition solution afterwards.The ink for ink-jet print that so obtains is 29.0% with the solid formation branch concentration of polymer composition solution, and pH is 9.2.
Adding pigment concentration to ink for ink-jet print in polymer composition solution 206.0 weight parts is the Cyanine Blue G-500pure-A480.0 weight part of 25 weight %, stirs 1 hour with the high speed dispersion device, obtains the colo(u)rant dispersion slip.
After this, utilize high-pressure homogenizer (miniature fluidizer) to repeat 20 this colo(u)rant dispersion slip and take turns dispersion, obtain dispersible pigment dispersion with the pressure of 200MPa.
Then, utilize separating centrifuge (05P-21) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, ink for ink-jet print is adjusted into pigment concentration with pigment dispersion reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration after, make the ink shown in the Table I-1 and form 13 ink for inkjet.
(example I-14)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, temperature sensor, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.
Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, methyl acrylate 66.6 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down at 80 ℃.
After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carry out reaction in 1 hour again with 80 ℃.
Utilize underpressure distillation remove diethylene glycol monomethyl ether thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% ink for ink-jet print polymer composition solution.
Then, in the separating flask of the 3000ml that has possessed whipping appts, return line, temperature sensor, dropping funnel, add polymer composition solution, in dropping funnel, add ion exchanged water 1454.0 weight parts and 30% aqueous sodium hydroxide solution, 346.0 weight parts, dripped in the clockwise separating flask with 20 minutes.
After dripping end, after having kept 30 minutes under 80 ℃, utilize underpressure distillation to remove methyl ethyl ketone, obtained polymer composition solution.The solid formation branch concentration of the polymer composition solution that so obtains is 30.5%, and pH is 9.1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 130mgKOH/g, and weight-average molecular weight is 32000.
Adding pigment concentration in polymer composition solution 197.0 weight parts is Cyanine Blue G-500pure-A 480.0 weight parts of 25 weight %, stirs 1 hour with the high speed dispersion device, obtains the colo(u)rant dispersion slip.
After this, utilize high-pressure homogenizer (miniature fluidizer) to repeat 20 this colo(u)rant dispersion slip and take turns dispersion, obtain dispersible pigment dispersion with the pressure of 200MPa.
Then, utilize separating centrifuge (05P-21) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, ink for ink-jet print is adjusted into pigment concentration with pigment dispersion reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration after, make the ink shown in the Table I-1 and form 14 ink for inkjet.
(reference example I-1)
Except substitutional crylic acid cyclohexyl 483.0 weight parts, and used beyond 2-EHA 483.0 weight parts, carried out in the same manner, made the ink for inkjet of the reference ink example 1 shown in the Table I-3 with embodiment 1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 38000.
(reference example I-2)
Except substitutional crylic acid cyclohexyl 483.0 weight parts, t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, and used beyond 2-ethylhexyl acrylate 483.0 weight parts, t-butylperoxy (2-ethylhexanoate) 16.8 weight parts, carry out in the same manner with embodiment 3, make the ink for inkjet of the reference ink example 2 shown in the Table I-3.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 8000.
(reference example I-3)
Except substitutional crylic acid cyclohexyl 483.0 weight parts, and used beyond lauryl acrylate 483.0 weight parts, carried out in the same manner, made the ink for inkjet of the reference ink example 3 shown in the table 3 with embodiment 1.In addition, get the part of ink for ink-jet print with polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 65mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 38000.
(reference example I-4)
Except substitutional crylic acid cyclohexyl 483.0 weight parts, t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, and used beyond lauryl acrylate 483.0 weight parts, t-butylperoxy (2-ethylhexanoate) 16.8 weight parts, carry out in the same manner with embodiment 3, make the ink for inkjet of the reference ink example 4 shown in the Table I-3.In addition, get the part of ink for ink-jet print with polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 65mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 8000.
(reference example I-5)
Except replacing pigment concentration is Cyanine Blue G-500pure-A 480.0 weight parts of 25 weight %, and used pigment concentration is Fast Yellow 7413-A 480.0 weight parts of 25 weight %, in addition, not to add ion exchanged water so that pigment concentration reaches the mode of 4 weight %, but so that pigment concentration reaches the mode of 6 weight % adds beyond the ion exchanged water, carry out in the same manner with reference example 4, make the ink for inkjet of the reference ink example 5 shown in the Table I-3.
(reference example I-6)
Except replacing pigment concentration is Cyanine Blue G-500pure-A 480.0 weight parts of 25 weight %, and used pigment concentration is the Pigment Violet GC227-A480.0 weight part of 25 weight %, in addition, not to add ion exchanged water so that pigment concentration reaches the mode of 4 weight %, but so that pigment concentration reaches the mode of 6 weight % adds beyond the ion exchanged water, carry out in the same manner with reference example 4, make the ink for inkjet of the reference ink example 6 shown in the Table I-3.
(reference example I-7)
Except t-butylperoxy (2-ethylhexanoate) 7.2 weight parts being made as 19.2 weight parts, carry out in the same manner with embodiment 3, make the ink for inkjet of the reference example 7 shown in the Table I-3.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 65mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 7000.
(reference example I-8)
Except with 2,4,7,9-tetramethyl--5-decine-4, the addition 0.15 weight % of 7-glycol is made as beyond the 0 weight %, carries out in the same manner with embodiment 2, makes the ink for inkjet of the reference example 8 shown in the Table I-4.
(reference example I-9)
Except with 2,4,7,9-tetramethyl--5-decine-4, the addition 0.15 weight % of 7-glycol is made as 0 weight %, with 1, the addition 3.5 weight % of 2-hexylene glycol are made as 0 weight %, triglycol 7 weight % are made as beyond the 10 weight %, carry out in the same manner, make the ink for inkjet of the reference example 9 shown in the Table I-4 with embodiment 2.
(reference example I-10)
Except with 2,4,7,9-tetramethyl--5-decine-4, the addition 0.15 weight % of 7-glycol is made as 0 weight %, and with 1, the addition 3.5 weight % of 2-hexylene glycol are made as 0 weight %, with 2-butyl-2-ethyl-1, ammediol 0.5% is made as 0%, in addition, triglycol 7 weight % is made as beyond the 10.5 weight %, carry out in the same manner with embodiment 2, make the ink for inkjet of the reference example 10 shown in the Table I-4.
(reference example I-11)
Except substitutional crylic acid 50.4 weight parts, become beyond 20 parts in the vinylformic acid, carry out in the same manner with embodiment 2, make the ink for inkjet of the reference example 11 shown in the table 4.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 25mgKOH/g, and weight-average molecular weight is 33000.
(reference example I-12)
Except substitutional crylic acid 50.4 weight parts, become beyond 133 parts in the vinylformic acid, carry out in the same manner with embodiment 2, make the ink for inkjet of the reference example 12 shown in the table 4.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 160mgKOH/g, and weight-average molecular weight is 32000.
(reference example I-13)
Except cyclohexyl acrylate 483.0 weight parts being become 242 parts of cyclohexyl acrylate 241.0 weight parts and lauryl acrylates, carry out in the same manner with embodiment 1, make the ink for inkjet of the reference example 13 shown in the Table I-4.
(reference example I-14)
Except benzyl acrylate 483.0 weight parts being become 242 parts of benzyl acrylate 241.0 weight parts and lauryl acrylates, carry out in the same manner with embodiment 1, make the ink for inkjet of the reference example 14 shown in the table 4.
(evaluation test 1: the evaluation method of the leakage profit on the common paper)
The ink for ink-jet print of embodiment in the example I 1～14 and reference example 1～14 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), the Word that utilizes Microsoft on XeroxP paper (Xerox of Fuji corporate system) obtains testing body with MS Ming Dynasty font, standard pattern (style), size 8 printing " Books " words.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this obtain enlarged photograph, will not have the literal banded partly to be evaluated as A fully, a position banded is evaluated as B, two position banded are evaluated as C, three above banded are evaluated as D.Its result is shown in Table I-1～Table I-4.
(evaluation test 2: the evaluation method of common paper color emissivity)
The ink for ink-jet print of embodiment in the example I 1～14 and reference example 1～14 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, obtain testing body.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag company (U.S.) system), measure OD value of all kinds.The result is as the value representation of OD value.
(evaluation test 3: the evaluation method of glossiness)
The ink for ink-jet print of embodiment in the example I 1～14 and reference example 1～14 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtain testing body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.Measure 20 degree gloss of this test body with glossmeter (HG-268, Suga trier Co., Ltd. system).Its result is shown in Table I-1～Table I-4.
(evaluation test 4: dispersed evaluation method)
Utilize laser particle size analysis device (Zetasizer 3000, Malvern company (Britain) system) to measure the median size of the particle in the ink for ink-jet print of embodiment 1～14 and reference example 1～6 in the example I.Its result is shown in Table I-1～Table I-4.
(evaluation test 5: the evaluation method of storage stability)
Utilize rolling-ball viscometer (rolling ball type viscosity meter) (AMVn, AntonPaar (Germany) corporate system) to measure in the example I ink for ink-jet print used among the embodiment 1～14 and reference example 1～14 with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in table 1～table 4.And, in the Table I-1～Table I-4, give making that used monomer composition, polymerization starter and pigment and ink for ink-jet print is fine in the ink for ink-jet print.
Table I-1
Table I-2
Table I-3
Figure BSA00000390083600451
Table I-4
Figure BSA00000390083600461
And the breviary symbol of expression is as follows in the Table I-1～Table I-4.
CHA: cyclohexyl acrylate
BZA: benzyl acrylate
MAA: methacrylic acid
AA: vinylformic acid
SMA: stearyl methacrylate
EHA: vinylformic acid (ethyl hexyl) ester
LA: lauryl acrylate
DEAEMA: methacrylic acid 2-(diethylamino) ethyl ester
HEMA: methacrylic acid 2-hydroxyl ethyl ester
BOEH: t-butylperoxy (2-ethylhexanoate)
AIBN: azobis isobutyronitrile
TDG:2,4,7,9-tetramethyl--5-decine-4,7-glycol
DOD:3,6-dimethyl-4-octyne-3,6-glycol
TDGEO10:2,4,7,9-tetramethyl--5-decine-4,10 moles of affixtures of the oxyethane of 7-glycol
DODEO4:3,6-dimethyl-4-octyne-3,4 moles of affixtures of the oxyethane of 6-glycol
1,2-HD:1,2-hexylene glycol
1,2-PH:1,2-pentanediol
TEGmBE: triglycol monobutyl ether
DEGmBE: diethylene glycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
The 2-P:2-pyrrolidone
GL: glycerine
TEG: triglycol
TMP: TriMethylolPropane(TMP)
TEA: trolamine
From the result of Table I-1 and Table I-2 as can be known, in the example I, under the situation of the ink for ink-jet print that has used embodiment 1～14, evaluation test 1～5 all is good result, yet under the situation of the ink for ink-jet print of the reference example 1～14 that has used Table I-3 and Table I-4, in certain or a plurality of project of test 1～5, can not obtain good result.
[example II]
(example II-1)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carry out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtain resin and form admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes, add Cyanine BlueG-500pure-A (C.I.PB 15:1 then with the high speed dispersion device; Adret pigment Co., Ltd. system) 480.0 weight parts stirred 1 hour with the high speed dispersion device, had obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.Made ink Table I-2 shown in and formed 1 ink for inkjet thereafter.
(example II-2)
Except substitutional crylic acid 50.4 weight parts, become beyond methacrylic acid 13.2 weight parts, vinylformic acid 36.5 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 2 shown in the Table II-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 60mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 32000.
(example II-3)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 42.6 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 3 shown in the Table II-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 55mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 48000.
(example II-4)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 77.5 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 4 shown in the Table II-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 29000.
(example II-5)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 93.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 5 shown in the Table II-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 120mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 34000.
(example II-6)
Except replacing pigment concentration is Cyanne Blue G-500pure-A 480.0 weight parts of 25 weight %, become Monarch 800 (C.I.PBk7:Cabot system) in addition, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 13 shown in the Table I-2.
(example II-7)
Except replacing pigment concentration is Cyanine Blue G-500pure-A 480.0 weight parts of 25 weight %, become Monarch 800 (C.I.PBk7:Cabot system) in addition, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example 14 shown in the Table II-2.
(example II-8)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used beyond Pigment Violet GC227-A 120.0 weight parts, carried out in the same manner, made the ink for inkjet of the composition example 19 shown in the Table II-2 with embodiment 1.
(example II-9)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used beyond Pigment Violet GC227-A 120.0 weight parts, carried out in the same manner, made the ink for inkjet of the composition example 20 shown in the Table II-2 with embodiment 2.
(example II-10)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used FastYellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 120.0 weight parts, carries out in the same manner, make the ink for inkjet of the composition example 25 shown in the Table II-2 with embodiment 1.
(example II-11)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used FastYellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 120.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example 26 shown in the Table II-2 with embodiment 2.
(reference example II-1)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 100.8 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 6 shown in the Table II-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 130mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 29000.
(reference example II-2)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 116.3 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 7 shown in the Table II-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 150mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 34000.
(reference example II-3)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 155.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 8 shown in the Table II-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 200mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 29000.
(reference example II-4)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 20.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 9 shown in the Table II-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 65mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 10000.
(reference example II-5)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 15.0 weight parts, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example 10 shown in the Table II-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 60mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 18000.
(reference example II-6)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 3.1 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 11 shown in the Table II-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 65mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 140000.
(reference example II-7)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 23.3 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 12 shown in the Table II-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 30mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 33000.
(reference example II-8)
Except replacing Cyanine B1ue G-500pure-A 480.0 weight parts, become beyond Monarch800 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example 15 shown in the Table II-2.
(reference example II-9)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch800 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 5, made the ink for inkjet of the composition example 16 shown in the Table II-2.
(reference example II-10)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch800 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 6, made the ink for inkjet of the composition example 17 shown in the Table II-2.
(reference example II-11)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch800 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 7, made the ink for inkjet of the composition example 18 shown in the Table II-2.
(reference example II-12)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the PigmentViolet GC227-A480.0 weight part, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example 21 shown in the Table II-2.
(reference example II-13)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the PigmentViolet GC227-A480.0 weight part, carry out in the same manner with reference example 5, made the ink for inkjet of the composition example 22 shown in the Table II-2.
(reference example II-14)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the PigmentViolet GC227-A480.0 weight part, carry out in the same manner with reference example 6, made the ink for inkjet of the composition example 23 shown in the Table II-2.
(reference example II-15)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the PigmentViolet GC227-A480.0 weight part, carry out in the same manner with reference example 7, made the ink for inkjet of the composition example 24 shown in the Table II-2.
(reference example II-16)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond FastYellow 7413-A 480.0 weight parts, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example 27 shown in the Table II-2.
(reference example II-17)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond FastYellow 7413-A 480.0 weight parts, carry out in the same manner with reference example 5, made the ink for inkjet of the composition example 28 shown in the Table II-2.
(reference example II-18)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond FastYellow 7413-A 480.0 weight parts, carry out in the same manner with reference example 6, made the ink for inkjet of the composition example 29 shown in the Table II-2.
(reference example II-19)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond FastYellow 7413-A 480.0 weight parts, carry out in the same manner with reference example 7, made the ink for inkjet of the composition example 30 shown in the Table II-2.
(evaluation test 1: the evaluation method of common paper color emissivity)
The ink for ink-jet print of embodiment in the example II 1～11 and reference example 1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, obtain testing body.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag company (U.S.) system), measure OD value of all kinds.The result as the value representation of OD value in Table II-1.
(evaluation test 2: the evaluation method of glossiness)
The ink for ink-jet print of embodiment in the example II 1～11 and reference example 1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).Its result is shown in the Table II-1.
(evaluation test 3: dispersed evaluation method)
Utilize laser particle size analysis device (Zetasizer 3000, Malvern company (Britain) system) to measure the median size of the particle in the ink for ink-jet print of embodiment 1～11 and reference example 1～19 in the example II.Its result is shown in the Table II-1.
(evaluation test 4: the evaluation method of storage stability)
Utilize rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) to measure in the example II ink for ink-jet print used among the embodiment 1～11 and reference example 1～19 with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table II-1.And, in the Table II-1, give monomer composition, polymerization starter and pigment and ink for ink-jet print used in the manufacturing ink for ink-jet print and form.
Figure BSA00000390083600551
Figure BSA00000390083600561
And the breviary symbol of expression is as follows in the Table II-1～2.
BZA: benzyl acrylate
AA: vinylformic acid
MAA: methacrylic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
PBk7:C.I. Pigment black 7 (carbon black)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PV19:C.I. pigment violet 19 (quinoline a word used for translation ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
BEPD:2-butyl-2-ethyl-1, ammediol
1,2-HD:1,2-hexylene glycol
TMP: TriMethylolPropane(TMP)
From the result of Table II-1 and Table II-2 as can be known, in the example II, under the situation of the ink for ink-jet print that has used embodiment 1～11, evaluation test 1～5 all is good result, yet under the situation of the ink for ink-jet print that has used reference example 1～18, in certain or a plurality of project of test 1～5, can not obtain good result.
[EXAMPLE III]
(EXAMPLE III-1)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carried out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtain resin and form admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes with the high speed dispersion device, then add 480.0 weight part green pigment C.I.PB15:1, stirred 1 hour with the high speed dispersion device, obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.Made ink Table III-2 shown in and formed 1 ink for inkjet thereafter.
(EXAMPLE III-2)
Except substitutional crylic acid 50.4 weight parts, become beyond methacrylic acid 13.2 weight parts, vinylformic acid 36.5 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 2 shown in the Table III-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 60mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 32000.
(EXAMPLE III-3)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 42.6 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 3 shown in the Table III-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 55mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 48000.
(EXAMPLE III-4)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 77.5 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 4 shown in the Table III-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 29000.
(EXAMPLE III-5)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 93.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 5 shown in the Table III-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 120mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 34000.
(EXAMPLE III-6)
Except being that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become 480.0 weight parts of black pigment C.I.PBk7 with pigment concentration, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 13 shown in the Table III-2.
(EXAMPLE III-7)
Except being that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become 480.0 weight parts of black pigment C.I.PBk7 with pigment concentration, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example 14 shown in the Table III-2.
(EXAMPLE III-8)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of magenta pigment C.I.PR122, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 19 shown in the Table III-2.
(EXAMPLE III-9)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of magenta pigment C.I.PR122, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example 20 shown in the Table III-2.
(EXAMPLE III-10)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of yellow ultramarine C.I.PY74, carry out in the same manner with embodiment 1, make the ink for inkjet of the composition example 25 shown in the Table III-2.
(EXAMPLE III-11)
Except 480.0 weight parts with green pigment C.I.PB15:1 become 480.0 weight parts of yellow ultramarine C.I.PY74, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example 26 shown in the Table III-2.
(reference example III-1)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 100.8 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 6 shown in the Table III-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 130mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 29000.
(reference example III-2)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 116.3 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 7 shown in the Table III-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 150mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 34000.
(reference example III-3)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 155.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 8 shown in the Table III-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 200mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 29000.
(reference example III-4)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 20.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 9 shown in the Table III-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 65mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 10000.
(reference example III-5)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 15.0 weight parts, carry out in the same manner with EXAMPLE III-2, made the ink for inkjet of the composition example 10 shown in the Table III-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 60mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 18000.
(reference example III-6)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 3.1 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 11 shown in the Table III-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 65mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 140000.
(reference example III-7)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 23.3 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 12 shown in the Table III-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 30mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 33000.
(reference example III-8)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of black pigment C.I.PBk7, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example 15 shown in the Table III-2.
(reference example III-9)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of black pigment C.I.PBk7, carry out in the same manner with reference example 5, made the ink for inkjet of the composition example 16 shown in the Table III-2.
(reference example III-10)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of black pigment C.I.PBk7, carry out in the same manner with reference example 6, made the ink for inkjet of the composition example 17 shown in the Table III-2.
(reference example III-11)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of black pigment C.I.PBk7, carry out in the same manner with reference example 7, made the ink for inkjet of the composition example 18 shown in the Table III-2.
(reference example III-12)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of magenta pigment C.I.PR122, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example 21 shown in the Table III-2.
(reference example III-13)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of magenta pigment C.I.PR122, carry out in the same manner with reference example 5, made the ink for inkjet of the composition example 22 shown in the Table III-2.
(reference example III-14)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of magenta pigment C.I.PR122, carry out in the same manner with reference example 6, made the ink for inkjet of the composition example 23 shown in the Table III-2.
(reference example III-15)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of magenta pigment C.I.PR122, carry out in the same manner with reference example 7, made the ink for inkjet of the composition example 24 shown in the Table III-2.
(reference example III-16)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of yellow ultramarine C.I.PY74, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example 27 shown in the Table III-2.
(reference example III-17)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of yellow ultramarine C.I.PY74, carry out in the same manner with reference example 5, made the ink for inkjet of the composition example 28 shown in the Table III-2.
(reference example III-18)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of yellow ultramarine C.I.PY74, carry out in the same manner with reference example 6, made the ink for inkjet of the composition example 29 shown in the Table III-2.
(reference example III-19)
Except 480.0 weight parts with green pigment C.I.PB 15:1 become 480.0 weight parts of yellow ultramarine C.I.PY74, carry out in the same manner with reference example 7, made the ink for inkjet of the composition example 30 shown in the Table III-2.
(evaluation test 1: the evaluation method of the leakage profit on the common paper)
The ink for ink-jet print of EXAMPLE III-1～11 and reference example III-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), the Word that utilizes Microsoft on XeroxP paper (Xerox of Fuji corporate system) has obtained the test body with MS Ming Dynasty font, standard pattern (style), size 8 printing " Books " words.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this obtain enlarged photograph, will not have the literal banded partly to be evaluated as A fully, a position banded is evaluated as B, two position banded are evaluated as C, three above banded are evaluated as D.Its result is shown in the Table III-1.
(evaluation test 2: the evaluation method of common paper color emissivity)
The ink for ink-jet print of EXAMPLE III-1～11 and reference example III-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, obtain testing body.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag company (U.S.) system), measure OD value of all kinds.The result as the value representation of OD value in Table III-1.
(evaluation test 3: the evaluation method of glossiness)
The ink for ink-jet print of EXAMPLE III-1～11 and reference example III-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.Measure 20 degree gloss of this test body with glossmeter (HG-268, Suga trier Co., Ltd. system).Its result is shown in the Table III-1.
(evaluation test 4: dispersed evaluation method)
(Zetasizer 3000 to utilize laser particle size analysis device, Malvern company (Britain) system) measured the median size of the particle in the ink for ink-jet print of EXAMPLE III-1～11 and reference example III-1～19, in addition, utilize infiltration type electron microscope (JEM-1230, NEC corporate system) to measure the one-level particle diameter of pigment particles.Its result is shown in the Table III-1.
(evaluation test 5: the evaluation method of storage stability)
Utilize rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) to measure ink for ink-jet print used in EXAMPLE III-1～11 and reference example III-1～19 with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mpas)/initial stage viscosity (mpas) after 1 week under 70 ℃ is in Table III-1.And, in the Table III-1, give monomer composition, polymerization starter and pigment and ink for ink-jet print used in the manufacturing ink for ink-jet print and form.
Figure BSA00000390083600651
Figure BSA00000390083600661
And the breviary symbol of expression is as follows in the Table III-1～Table III-2.
BZA: benzyl acrylate
AA: vinylformic acid
MAA: methacrylic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
PBk7:C.I. Pigment black 7 (carbon black)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PV19:C.I. pigment violet 19 (quinoline a word used for translation ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
1,2-HD:1,2-hexylene glycol
From the result of Table III-1 and Table III-2 as can be known, under the situation of the ink for ink-jet print that has used EXAMPLE III-1～11, evaluation test 1～5 all is good result, yet under the situation of the ink for ink-jet print that has used reference example III-1～19, in certain or a plurality of project of evaluation test 1～5, or not good result.
[EXAMPLE IV]
(EXAMPLE IV-1)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carried out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes with the high speed dispersion device, then add 480.0 weight part green pigment C.I.PB15:1, stirred 1 hour with the high speed dispersion device, obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, from the dispersible pigment dispersion that so obtains, utilize the underpressure distillation used vaporizer remove methyl ethyl ketone and water-part, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.Made ink Table IV-2 shown in and formed 1 ink for inkjet thereafter.
(EXAMPLE IV-2)
Except 1.0 parts of the TriMethylolPropane(TMP)s in the ink for ink-jet print that replaces composition example 1, and 3.0 parts of TriMethylolPropane(TMP)s have been added, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carried out in the same manner, modulated the ink for inkjet shown in the composition example 2 of Table IV-2 with embodiment 1.
(EXAMPLE IV-3)
Except 1.0 parts of the TriMethylolPropane(TMP)s in the ink for ink-jet print that replaces composition example 1, and 5.0 parts of TriMethylolPropane(TMP)s have been added, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, modulated the ink for inkjet shown in the composition example 3 of Table IV-2.
(EXAMPLE IV-4)
Except 1.0 parts of the TriMethylolPropane(TMP)s in the ink for ink-jet print that replaces composition example 1, and 10.0 parts of TriMethylolPropane(TMP)s have been added, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carried out in the same manner, modulated the ink for inkjet shown in the composition example 4 of Table IV-2 with embodiment 1.
(EXAMPLE IV-5)
Except 1.0 parts of the TriMethylolPropane(TMP)s in the ink for ink-jet print that replaces composition example 1, and 15.0 parts of TriMethylolPropane(TMP)s have been added, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carried out in the same manner, modulated the ink for inkjet shown in the composition example 5 of Table IV-2 with embodiment 1.
(EXAMPLE IV-6)
Except 1.0 parts of the TriMethylolPropane(TMP)s in the ink for ink-jet print that replaces composition example 1, and 20.0 parts of TriMethylolPropane(TMP)s have been added, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carried out in the same manner, modulated the ink for inkjet shown in the composition example 6 of Table IV-2 with embodiment 1.
(EXAMPLE IV-7)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 11 shown in the Table IV-2.
(EXAMPLE IV-8)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example 12 shown in the Table IV-2.
(EXAMPLE IV-9)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 3, made the ink for inkjet of the composition example 13 shown in the Table IV-2.
(EXAMPLE IV-10)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 4, made the ink for inkjet of the composition example 14 shown in the Table IV-2.
(EXAMPLE IV-11)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example 15 shown in the Table IV-2.
(EXAMPLE IV-12)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 6, made the ink for inkjet of the composition example 16 shown in the Table IV-2.
(EXAMPLE IV-13)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 21 shown in the Table IV-2.
(EXAMPLE IV-14)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example 22 shown in the Table IV-2.
(EXAMPLE IV-15)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 3, made the ink for inkjet of the composition example 23 shown in the Table IV-2.
(EXAMPLE IV-16)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 4, made the ink for inkjet of the composition example 24 shown in the Table IV-2.
(EXAMPLE IV-17)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example 25 shown in the Table IV-2.
(EXAMPLE IV-18)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 6, made the ink for inkjet of the composition example 26 shown in the Table IV-2.
(EXAMPLE IV-19)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 31 shown in the Table IV-2.
(EXAMPLE IV-20)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example 32 shown in the Table IV-2.
(EXAMPLE IV-21)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 3, made the ink for inkjet of the composition example 33 shown in the Table IV-2.
(EXAMPLE IV-22)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 4, made the ink for inkjet of the composition example 34 shown in the Table IV-2.
(EXAMPLE IV-23)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example 35 shown in the Table IV-2.
(EXAMPLE IV-24)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 6, made the ink for inkjet of the composition example 36 shown in the Table IV-2.
(reference example IV-1)
Except removing the TriMethylolPropane(TMP) in the ink for ink-jet print of forming example 1, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, modulated the ink for inkjet shown in the composition example 7 of Table IV-2.
(reference example IV-2)
Except 1.0 parts of the TriMethylolPropane(TMP)s in the ink for ink-jet print that replaces composition example 1, and added 0.5 part of TriMethylolPropane(TMP), and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, modulated the ink for inkjet shown in the composition example 8 of Table IV-2.
(reference example IV-3)
Except 1.0 parts of the TriMethylolPropane(TMP)s in the ink for ink-jet print that replaces composition example 1, and 25.0 parts of TriMethylolPropane(TMP)s have been added, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carried out in the same manner, modulated the ink for inkjet shown in the composition example 9 of Table IV-2 with embodiment 1.
(reference example IV-4)
Except 1.0 parts of the TriMethylolPropane(TMP)s in the ink for ink-jet print that replaces composition example 1, and 30.0 parts of TriMethylolPropane(TMP)s have been added, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carried out in the same manner, modulated the ink for inkjet shown in the composition example 10 of Table IV-2 with embodiment 1.
(reference example IV-5)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 1, made the ink for inkjet shown in the composition example 17 of Table IV-2.
(reference example IV-6)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example 18 shown in the Table IV-2.
(reference example IV-7)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 3, made the ink for inkjet of the composition example 19 shown in the Table IV-2.
(reference example IV-8)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 4, made the ink for inkjet of the composition example 20 shown in the Table IV-2.
(reference example IV-9)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example 27 shown in the Table IV-2.
(reference example IV-10)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example 28 shown in the Table IV-2.
(reference example IV-11)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 3, made the ink for inkjet of the composition example 29 shown in the Table IV-2.
(reference example IV-12)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 4, made the ink for inkjet of the composition example 30 shown in the Table IV-2.
(reference example IV-13)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example 37 shown in the Table IV-2.
(reference example IV-14)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example 38 shown in the Table IV-2.
(reference example IV-15)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 3, made the ink for inkjet of the composition example 39 shown in the Table IV-2.
(reference example IV-16)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 4, made the ink for inkjet of the composition example 40 shown in the Table IV-2.
(evaluation test 1: shower nozzle stops up the evaluation method of Restoration)
Behind the ink for ink-jet print of in print cartridge, having filled EXAMPLE IV-1～24 and reference example IV-1～16, be installed on the ink-jet printer (EC-930C, Seiko Epson Corp's system), after having placed 12 months under 50 ℃ the dry environment, print and stop up the check pattern, ratio with 1 time/manually cleans, until spray ink from whole nozzles, instrumentation whole nozzles several times the time restore.Printing model is with print paper: common paper, print quality: hyperfine, color correct: do not have, Print direction: two-way and carry out, to clean manually that restorative is evaluated as A when being 1～3 time, to clean manually that restorative is evaluated as B when being 4～6 times, will clean manually that restorative is evaluated as C when being 7～9 times, with till restoring manually cleaning be more than 10 times or can't be evaluated as D by restorative.Its result is shown in the Table IV-1.
(evaluation test 2: the evaluation method of ink accumulation property)
The ink for ink-jet print of EXAMPLE IV-1～24 and reference example IV-1～16 is used ink-jet printer (PX-V600, Seiko Epson Corp's system) printed continuously 3000 boundless printings on the spot of all kinds with pattern after, utilize visual instrumentation ink throwing the accumulation level of beating in the zone.Printing model is with print paper: common paper, print quality: photo, color correct: do not have, Print direction: single direction and carrying out, to can't see the A that is evaluated as of stain on the print less than piling up,, will produce the C that is evaluated as of stain on the print because of accumulation though yet the B that is evaluated as that piles up the stain can't see on the print will be seen.Its result is shown in the Table IV-1.
(evaluation test 3: the evaluation method of common paper color emissivity)
The ink for ink-jet print of EXAMPLE IV-1～24 and reference example IV-1～16 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, obtain testing body.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag company (U.S.) system), measure OD value of all kinds.The result is as the value representation of OD value.
(evaluation test 4: the evaluation method of glossiness)
The ink for ink-jet print of EXAMPLE IV-1～24 and reference example IV-1～16 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.Measure 20 degree gloss of this test body with glossmeter (HG-268, Suga trier Co., Ltd. system).Its result is shown in the Table IV-1.
(evaluation test 5: dispersed evaluation method)
Utilize laser particle size analysis device (Zetasizer 3000, Malvern company (Britain) system) to measure the median size of the particle in the ink for ink-jet print of EXAMPLE IV-1～24 and reference example IV-1～16.Its result is shown in the Table IV-1.
(evaluation test 6: the evaluation method of storage stability)
Utilize rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) to measure ink for ink-jet print used in EXAMPLE IV-1～24 and reference example IV-1～16 with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table IV-1.And, in the Table IV-1, give monomer composition, polymerization starter and pigment and ink for ink-jet print used in the manufacturing ink for ink-jet print and form.
Figure BSA00000390083600771
Figure BSA00000390083600781
And the breviary symbol of expression is as follows in the Table IV-1～Table IV-2.
BZA: benzyl acrylate
AA: vinylformic acid
MAA: methacrylic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
PBk7:C.I. Pigment black 7 (carbon black)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PR122:C.I. pigment red 122 (quinoline a word used for translation ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
1,2-HD:1,2-hexylene glycol
TMP: TriMethylolPropane(TMP)
From the result of Table IV-1 and Table IV-2 as can be known, under the situation of the ink for ink-jet print that has used EXAMPLE IV-1～24, evaluation test 1～6 all is good result, yet under the situation of the ink for ink-jet print that has used reference example IV-1～16, in certain or a plurality of project of evaluation test 1～6, or not good result.
[EXAMPLE V]
(EXAMPLE V-1)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carried out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes with the high speed dispersion device, then add 480.0 weight part green pigment C.I.PB15:1, stirred 1 hour with the high speed dispersion device, obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.Made ink Table V-2 shown in and formed 1 ink for inkjet thereafter.
(EXAMPLE V-2)
Except replacing the 2-butyl-2-ethyl-1 in the ink for ink-jet print of forming example 1,0.1 part of ammediol, and added 2-butyl-2-ethyl-1,0.5 part of ammediol, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, modulated the ink for inkjet shown in the composition example 2 of Table V-2.
(EXAMPLE V-3)
Except replacing the 2-butyl-2-ethyl-1 in the ink for ink-jet print of forming example 1,0.1 part of ammediol, and added 2-butyl-2-ethyl-1,1.0 parts of ammediols, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, modulated the ink for inkjet shown in the composition example 3 of Table V-2.
(EXAMPLE V-4)
Except replacing the 2-butyl-2-ethyl-1 in the ink for ink-jet print of forming example 1,0.1 part of ammediol, and added 2-butyl-2-ethyl-1,2.0 parts of ammediols, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, modulated the ink for inkjet shown in the composition example 4 of Table V-2.
(EXAMPLE V-5)
Except replacing the 2-butyl-2-ethyl-1 in the ink for ink-jet print of forming example 1,0.1 part of ammediol, and added 2-butyl-2-ethyl-1,3.0 parts of ammediols, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, modulated the ink for inkjet shown in the composition example 5 of Table V-2.
(EXAMPLE V-6)
Except replacing the 2-butyl-2-ethyl-1 in the ink for ink-jet print of forming example 1,0.1 part of ammediol, and added 2-butyl-2-ethyl-1,5.0 parts of ammediols, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, modulated the ink for inkjet shown in the composition example 6 of Table V-2.
(EXAMPLE V-7)
Except replacing the 2-butyl-2-ethyl-1 in the ink for ink-jet print of forming example 1,0.1 part of ammediol, and added 2-butyl-2-ethyl-1,10.0 parts of ammediols, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, modulated the ink for inkjet shown in the composition example 7 of Table V-2.
(EXAMPLE V-8)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 10 shown in the Table V-2.
(EXAMPLE V-9)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB 15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example 11 shown in the Table V-2.
(EXAMPLE V-10)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 3, made the ink for inkjet of the composition example 12 shown in the Table V-2.
(EXAMPLE V-11)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 4, made the ink for inkjet of the composition example 13 shown in the Table V-2.
(EXAMPLE V-12)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example 14 shown in the Table V-2.
(EXAMPLE V-13)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 6, made the ink for inkjet of the composition example 15 shown in the Table V-2.
(EXAMPLE V-14)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 7, made the ink for inkjet of the composition example 16 shown in the Table V-2.
(EXAMPLE V-15)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 19 shown in the Table V-2.
(EXAMPLE V-16)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example 20 shown in the Table V-2.
(EXAMPLE V-17)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 3, made the ink for inkjet of the composition example 21 shown in the Table V-2.
(EXAMPLE V-18)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 4, made the ink for inkjet of the composition example 22 shown in the Table V-2.
(EXAMPLE V-19)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example 23 shown in the Table V-2.
(EXAMPLE V-20)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 6, made the ink for inkjet of the composition example 24 shown in the Table V-2.
(EXAMPLE V-21)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 7, made the ink for inkjet of the composition example 25 shown in the Table V-2.
(EXAMPLE V-22)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example 28 shown in the Table V-2.
(EXAMPLE V-23)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example 29 shown in the Table V-2.
(EXAMPLE V-24)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 3, made the ink for inkjet of the composition example 30 shown in the Table V-2.
(EXAMPLE V-25)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 4, made the ink for inkjet of the composition example 31 shown in the Table V-2.
(EXAMPLE V-26)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example 32 shown in the Table V-2.
(EXAMPLE V-27)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 6, made the ink for inkjet of the composition example 33 shown in the Table V-2.
(EXAMPLE V-28)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 7, made the ink for inkjet of the composition example 34 shown in the Table V-2
(reference example V-1)
Except removing the 2-butyl-2-ethyl-1 in the ink for ink-jet print of forming example 1, ammediol, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity carries out in the same manner with embodiment 1, has modulated the ink for inkjet shown in the composition example 8 of Table V-2.
(reference example V-2)
Except replacing the 2-butyl-2-ethyl-1 in the ink for ink-jet print of forming example 1,0.1 part of ammediol, and added 2-butyl-2-ethyl-1,15.0 parts of ammediols, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with embodiment 1, modulated the ink for inkjet shown in the composition example 9 of Table V-2.
(reference example V-3)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example 17 shown in the Table V-2.
(reference example V-4)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become black pigment C.I.PBk7, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example 18 shown in the Table V-2.
(reference example V-5)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example 26 shown in the Table V-2.
(reference example V-6)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become magenta pigment C.I.PR122, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example 27 shown in the Table V-2.
(reference example V-7)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example 35 shown in the Table V-2.
(reference example V-8)
Except with pigment concentration being 480.0 weight parts that 480.0 weight parts of the green pigment C.I.PB15:1 of 25 weight % become yellow ultramarine C.I.PY74, and increased and decreased beyond the amounts of glycerol in order to adjust viscosity, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example 36 shown in the Table V-2.
(evaluation test 1: the evaluation method of the leakage profit on the common paper)
The ink for ink-jet print of EXAMPLE V-1～28 and reference example V-1～8 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), the Word that utilizes Microsoft on XeroxP paper (Xerox of Fuji corporate system) has obtained the test body with MS Ming Dynasty font, standard pattern (style), size 8 printing " Books " words.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this obtain enlarged photograph, will not have the literal banded partly to be evaluated as A fully, a position banded is evaluated as B, two position banded are evaluated as C, three above banded are evaluated as D.Its result is shown in the Table V-1.
(evaluation test 2: the evaluation method of common paper color emissivity)
The ink for ink-jet print of EXAMPLE V-1～28 and reference example V-1～8 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, obtain testing body.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag company (U.S.) system), measure OD value of all kinds.The result as the value representation of OD value in Table V-1.
(evaluation test 3: the evaluation method of glossiness)
The ink for ink-jet print of EXAMPLE V-1～28 and reference example V-1～8 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).Its result is shown in the Table V-1.
(evaluation test 4: dispersed evaluation method)
Utilize laser particle size analysis device (Zetasizer 3000, Ma1vern company (Britain) system) to measure the median size of the particle in the ink for ink-jet print of EXAMPLE V-1～28 and reference example V-1～8.Its result is shown in the Table V-1.
(evaluation test 5: the evaluation method of storage stability)
Utilize ink for ink-jet print that rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) measured EXAMPLE V-1～28 and reference example V-1～8 with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table V-1.And, in the Table V-1, give monomer composition, polymerization starter and pigment and ink for ink-jet print used in the manufacturing ink for ink-jet print and form.
Figure BSA00000390083600881
Figure BSA00000390083600891
And the breviary symbol of expression is as follows in the Table V-1～Table V-2.
BZA: benzyl acrylate
AA: vinylformic acid
MAA: methacrylic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
PBk7:C.I. Pigment black 7 (carbon black)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PR122:C.I. pigment red 122 (quinoline a word used for translation ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
BEPD:2-butyl-2-ethyl-1, ammediol
1,2-HD:1,2-hexylene glycol
TMP: TriMethylolPropane(TMP)
From the result of Table V-1 and Table V-2 as can be known, under the situation of the ink for ink-jet print that has used EXAMPLE V-1～28, evaluation test 1～5 all is good result, yet under the situation of the ink for ink-jet print that has used reference example V-1～8, in certain or a plurality of project of evaluation test 1～5, or not good result.
[example VI]
(example VI-1)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, vinylformic acid 77.5 weight parts and t-butylperoxy (2-ethylhexanoate) 7.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carried out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 100mgKOH/g, and weight-average molecular weight is 22000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes with the high speed dispersion device, stirred 5 minutes with the high speed dispersion device again, adding pigment concentration then is the Cyanine Blue G-500pure-A (C.I.PB15:1 of 25 weight %; Adret pigment Co., Ltd. system) 480.0 weight parts stirred 1 hour with the high speed dispersion device, had obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.
Made ink for inkjet that ink Table VI-2 shown in form routine A thereafter.
(example VI-2)
Except the amount by the methyl ethyl ketone that will be added is made as 2040 weight parts, and the modulation resin forms admittedly and is divided into 22.7% polymer composition solution, the addition that is added to the polymer composition solution in the pigment is made as beyond 264.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(example VI-3)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts, and added beyond t-butylperoxy (2-ethylhexanoate) 3.5 weight parts, carried out in the same manner, modulated the ink for inkjet of the composition example A shown in the Table VI-2 with embodiment 1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 48000.
(example VI-4)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts, and t-butylperoxy (2-ethylhexanoate) 3.5 weight parts have been added, add 2040 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 22.7% polymer composition solution, and the addition that will be added to the polymer composition solution in the pigment is made as beyond 264.0 weight parts, carry out in the same manner with embodiment 1, modulated the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 48000.
(example VI-5)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts, and t-butylperoxy (2-ethylhexanoate) 3.2 weight parts have been added, add 1200 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 33.3% polymer composition solution, the addition that is added to the polymer composition solution in the pigment is made as beyond 180.0 weight parts, carry out in the same manner with embodiment 1, modulated the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 52000.
(example VI-6)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts, and t-butylperoxy (2-ethylhexanoate) 3.2 weight parts have been added, add 3360 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 15.1% polymer composition solution, and the addition that will be added to the polymer composition solution in the pigment is made as beyond 396.0 weight parts, carry out in the same manner with embodiment 1, modulated the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 52000.
(example VI-7)
Except substitutional crylic acid benzyl ester 483.0 weight parts, and 966.0 weight parts have been added, substitutional crylic acid 77.5 weight parts, and 155.0 weight parts have been added, substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts in addition, and t-butylperoxy (2-ethylhexanoate) 2.9 weight parts have been added, add 1200 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 33.3% polymer composition solution, and the addition that will be added to the polymer composition solution in the pigment is made as beyond 180.0 weight parts, carry out in the same manner with embodiment 1, modulated the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(example VI-8)
Except substitutional crylic acid benzyl ester 483.0 weight parts, and 966.0 weight parts have been added, substitutional crylic acid 77.5 weight parts, and 155.0 weight parts have been added, substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts in addition, and t-butylperoxy (2-ethylhexanoate) 2.9 weight parts have been added, add 3360 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 15.1% polymer composition solution, the addition that is added to the polymer composition solution in the pigment is made as beyond 396.0 weight parts, carry out in the same manner with embodiment 1, modulated the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(example VI-9)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example B shown in the Table VI-2.
(example VI-10)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example B shown in the Table VI-2.
(example VI-11)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 3, made the ink for inkjet of the composition example B shown in the Table VI-2.
(example VI-12)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 4, made the ink for inkjet of the composition example B shown in the Table VI-2.
(example VI-13)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example B shown in the Table VI-2.
(example VI-14)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 6, made the ink for inkjet of the composition example B shown in the Table VI-2.
(example VI-15)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 7, made the ink for inkjet of the composition example B shown in the Table VI-2.
(example VI-16)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 8, made the ink for inkjet of the composition example B shown in the Table VI-2.
(example VI-17)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example C shown in the Table VI-2.
(example VI-18)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example C shown in the Table VI-2.
(example VI-19)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 3, made the ink for inkjet of the composition example C shown in the Table VI-2.
(example VI-20)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 4, made the ink for inkjet of the composition example C shown in the Table VI-2.
(example VI-21)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example C shown in the Table VI-2.
(example VI-22)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 6, made the ink for inkjet of the composition example C shown in the Table VI-2.
(example VI-23)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 7, made the ink for inkjet of the composition example C shown in the Table VI-2.
(example VI-24)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 8, made the ink for inkjet of the composition example C shown in the Table VI-2.
(example VI-25)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with embodiment 1.
(example VI-26)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with embodiment 2.
(example VI-27)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with embodiment 3.
(example VI-28)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with embodiment 4.
(example VI-29)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with embodiment 5.
(example VI-30)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with embodiment 6.
(example VI-31)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with embodiment 7.
(example VI-32)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the FastYellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with embodiment 8.
(reference example VI-1)
Except the amount by the methyl ethyl ketone that will be added is made as 480 weight parts, and the modulation resin forms admittedly and is divided into 55.6% polymer composition solution, the addition that is added to the polymer composition solution in the pigment is made as beyond 108.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(reference example VI-2)
Except the amount by the methyl ethyl ketone that will be added is made as 2400 weight parts, and the modulation resin forms admittedly and is divided into 20.0% polymer composition solution, the addition that is added to the polymer composition solution in the pigment is made as beyond 300.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(reference example VI-3)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts, and t-butylperoxy (2-ethylhexanoate) 3.5 weight parts have been added, add 480 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 55.6% polymer composition solution, and the addition that will be added to the polymer composition solution in the pigment is made as beyond 108.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 48000.
(reference example VI-4)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts, and t-butylperoxy (2-ethylhexanoate) 3.5 weight parts have been added, add 2400 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 20.0% polymer composition solution, and the addition that will be added to the polymer composition solution in the pigment is made as beyond 300.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 48000.
(reference example VI-5)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts, and t-butylperoxy (2-ethylhexanoate) 3.2 weight parts have been added, add 1080 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 35.7% polymer composition solution, the addition that is added to the polymer composition solution in the pigment is made as beyond 168.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 52000.
(reference example VI-6)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts, and t-butylperoxy (2-ethylhexanoate) 3.2 weight parts have been added, add 3840 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 13.5% polymer composition solution, the addition that is added to the polymer composition solution in the pigment is made as beyond 444.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 52000.
(reference example VI-7)
Except substitutional crylic acid benzyl ester 483.0 weight parts, and 966.0 weight parts have been added, substitutional crylic acid 77.5 weight parts, and 155.0 weight parts have been added, substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts in addition, and t-butylperoxy (2-ethylhexanoate) 2.9 weight parts have been added, add 1080 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 35.7% polymer composition solution, and the addition that will be added to the polymer composition solution in the pigment is made as beyond 168.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(reference example VI-8)
Except substitutional crylic acid benzyl ester 483.0 weight parts, and 966.0 weight parts have been added, substitutional crylic acid 77.5 weight parts, and 155.0 weight parts have been added, substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts in addition, and t-butylperoxy (2-ethylhexanoate) 2.9 weight parts have been added, add 3840 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 13.5% polymer composition solution, and the addition that will be added to the polymer composition solution in the pigment is made as beyond 444.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(reference example VI-9)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts, and added beyond t-butylperoxy (2-ethylhexanoate) 9.3 weight parts, carried out in the same manner, made the ink for inkjet of the composition example A shown in the Table VI-2 with embodiment 1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 18000.
(reference example VI-10)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts, and t-butylperoxy (2-ethylhexanoate) 9.3 weight parts have been added, add 2040 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 22.7% polymer composition solution, the addition that is added to the polymer composition solution in the pigment is made as beyond 264.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 18000.
(reference example VI-11)
Except substitutional crylic acid benzyl ester 483.0 weight parts, and 966.0 weight parts have been added, substitutional crylic acid 77.5 weight parts, and 155.0 weight parts have been added, substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts in addition, and t-butylperoxy (2-ethylhexanoate) 2.6 weight parts have been added, add 1200 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 33.3% polymer composition solution, and the addition that will be added to the polymer composition solution in the pigment is made as beyond 180.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 130000.
(reference example VI-12)
Except substitutional crylic acid benzyl ester 483.0 weight parts, and 966.0 weight parts have been added, substitutional crylic acid 77.5 weight parts, and 155.0 weight parts have been added, substituted tert-butyl peroxy (2-ethylhexanoate) 7.8 weight parts in addition, and t-butylperoxy (2-ethylhexanoate) 2.6 weight parts have been added, add 3360 weight part methyl ethyl ketones in addition, the modulation resin forms admittedly and is divided into 15.1% polymer composition solution, and the addition that will be added to the polymer composition solution in the pigment is made as beyond 396.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 130000.
(reference example VI-13)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example B shown in the Table VI-2.
(reference example VI-14)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example B shown in the Table VI-2.
(reference example VI-15)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 3, made the ink for inkjet of the composition example B shown in the Table VI-2.
(reference example VI-16)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 4, made the ink for inkjet of the composition example B shown in the Table VI-2.
(reference example VI-17)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 5, made the ink for inkjet of the composition example B shown in the Table VI-2.
(reference example VI-18)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 6, made the ink for inkjet of the composition example B shown in the Table VI-2.
(reference example VI-19)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 7, made the ink for inkjet of the composition example B shown in the Table VI-2.
(reference example VI-20)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 8, made the ink for inkjet of the composition example B shown in the Table VI-2.
(reference example VI-21)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example C shown in the Table VI-2.
(reference example VI-22)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example C shown in the Table VI-2.
(reference example VI-23)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 3, made the ink for inkjet of the composition example C shown in the Table VI-2.
(reference example VI-24)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 4, made the ink for inkjet of the composition example C shown in the Table VI-2.
(reference example VI-25)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 5, made the ink for inkjet of the composition example C shown in the Table VI-2.
(reference example VI-26)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 6, made the ink for inkjet of the composition example C shown in the Table VI-2.
(reference example VI-27)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 7, made the ink for inkjet of the composition example C shown in the Table VI-2.
(reference example VI-28)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment VIolet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 8, made the ink for inkjet of the composition example C shown in the Table VI-2.
(reference example VI-29)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with reference example 1.
(reference example VI-30)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with reference example 2.
(reference example VI-31)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with reference example 3.
(reference example VI-32)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with reference example 4.
(reference example VI-33)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with reference example 5.
(reference example VI-34)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with reference example 6.
(reference example VI-35)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with reference example 7.
(reference example VI-36)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table VI-2 with reference example 8.
(evaluation test 1: the evaluation method of common paper color emissivity)
The ink for ink-jet print of example VI-1～32 and reference example VI-1～36 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, obtain testing body.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag company (U.S.) system), measure OD value of all kinds.The result as the value representation of OD value in Table VI-1.
(evaluation test 2: the evaluation method of glossiness)
The ink for ink-jet print of example VI-1～32 and reference example VI-1～36 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).Its result is shown in the Table VI-1.
(evaluation test 3: dispersed evaluation method)
Utilize laser particle size analysis device (Zetasizer 3000, Malvern company (Britain) system) to measure the median size of the particle in the ink for ink-jet print of example VI-1～32 and reference example VI-1～36.Its result is shown in the Table VI-1.
(evaluation test 4: the evaluation method of storage stability)
Utilize rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) to measure ink for ink-jet print used in example VI-1～32 and reference example VI-1～36 with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table VI-1.And, in the Table VI-1, give monomer composition, polymerization starter and pigment and ink for ink-jet print used in the manufacturing ink for ink-jet print and form.
Figure BSA00000390083601051
Figure BSA00000390083601061
Table VI-2
Form example A B C D
P?B?15:1 4 - - -
P?B?k?7 - 5 - -
P?V?19 - - 5 -
P?Y?74 - - - 5
D?E?G?m?B?E 0.2 - 0.3 -
T?E?G?m?B?E 1 3 1 1
P?G?m?B?E - - - 0.1
D?P?G?m?B?E 0.1 - - -
B?E?P?D 0.7 0.7 0.7 0.7
1、2-H?D 4 3 4 4
Glycerine 15 10 10 10
T?M?P 7 4 5 5
Alkene E 1010 0.1 0.1 - -
Surfynol?104 0.15 0.15 0.15 0.15
E D T A 2.0% aqueous solution 1 1 1 1
Ion exchanged water Residual amount Residual amount Residual amount Residual amount
And the breviary symbol of expression is as follows in the Table VI-1～Table VI-2.
BZA: benzyl acrylate, AA: vinylformic acid, BPEH: t-butylperoxy (2-ethylhexanoate), PBk7:C.I. Pigment black 7 (carbon black), PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine), PV19:C.I. pigment violet 19 (quinoline a word used for translation ketone), PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment), DEGmBE: diethylene glycol monobutyl ether, TEGmBE: triglycol monobutyl ether, PGmBE: propylene glycol monobutyl ether, DPGmBE: dipropylene glycol monobutyl ether, BEPD:2-butyl-2-ethyl-1, ammediol, 1,2-HD:1, the 2-hexylene glycol, TMP: TriMethylolPropane(TMP), EDTA: disodium ethylene diamine tetraacetate
From the result of Table VI-1 and Table VI-2 as can be known, under the situation of the ink for ink-jet print that has used example VI-1～32, evaluation test 1～5 all is good result, yet under the situation of the ink for ink-jet print that has used reference example VI-1～36, in certain or a plurality of project of evaluation test 1～5, or not good result.
[example VII A]
[modulation of resin emulsion]
[resin emulsion A]
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carried out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
Then, used the underpressure distillation of vaporizer to remove methyl ethyl ketone the polymer composition soln using of so making, after being cooled to normal temperature, add ion exchanged water and 5% aqueous sodium hydroxide solution, having formed resinous principle is that 40 weight %, pH are 8 resin emulsion.Utilize laser particle size analysis device (Zetasizer3000, Malvern corporate system) to measure the median size of this emulsion, its result is 55nm.
[resin emulsion B]
Except substitutional crylic acid 50.4 weight parts, become beyond methacrylic acid 13.2 weight parts, vinylformic acid 36.5 weight parts, carry out in the same manner with resin emulsion A, modulated resin emulsion B.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 60mgKOH/g with the acid number of the solid substance of polymer composition, weight-average molecular weight is 32000, and the median size of this emulsion is 62nm.
[resin emulsion C]
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 42.6 weight parts, carry out in the same manner with resin emulsion A, modulated resin emulsion C.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 55mgKOH/g with the acid number of the solid substance of polymer composition, weight-average molecular weight is 48000, and the median size of this emulsion is 58nm.
[resin emulsion D]
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 77.5 weight parts, carry out in the same manner with resin emulsion A, modulated resin emulsion D.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, weight-average molecular weight is 29000, and the median size of this emulsion is 48nm.
[resin emulsion E]
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 93.0 weight parts, carry out in the same manner with resin emulsion A, modulated resin emulsion E.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 120mgKOH/g with the acid number of the solid substance of polymer composition, weight-average molecular weight is 34000, and the median size of this emulsion is 43nm.
[resin emulsion F]
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 155.0 weight parts, carry out in the same manner with resin emulsion A, modulated resin emulsion F.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 200mgKOH/g with the acid number of the solid substance of polymer composition, weight-average molecular weight is 29000, and the median size of this emulsion is 38nm.
[resin emulsion G]
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 19.2 weight parts, carry out in the same manner with resin emulsion A, modulated resin emulsion G.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 65mgKOH/g with the acid number of the solid substance of polymer composition, weight-average molecular weight is 10000, and the median size of this emulsion is 65nm.
[resin emulsion H]
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 2.3 weight parts, carry out in the same manner with resin emulsion A, modulated resin emulsion G.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 65mgKOH/g with the acid number of the solid substance of polymer composition, weight-average molecular weight is 140000, and the median size of this emulsion is 78nm.
[resin emulsion I]
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add ion exchanged water 300.0 weight parts and Sodium Lauryl Sulphate BP/USP 1 weight part, when stirring, be warmed up to 70 ℃.Add Potassium Persulphate 1.3 weight parts and after dissolving as polymerization starter, to stir ion exchanged water 150 weight parts, Sodium Lauryl Sulphate BP/USP 1 weight part, acrylamide 7 weight parts, methyl methacrylate 225 weight parts, butyl acrylate 78 weight parts and methacrylic acid 10 weight parts in advance and solution add dropping funnel, dripped in separating flask with 4 hours down and make it to react at 70 ℃.After finishing to drip, under 70 ℃, kept 3 hours again.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 75mgKOH/g, and weight-average molecular weight is 44000.
The polymer composition solution of so making is cooled to normal temperature, adds ion exchanged water and 5% aqueous sodium hydroxide solution, having formed resinous principle is that 40 weight %, pH are 8 resin emulsion.Utilize laser particle size analysis device (Zetasizer3000, Malvern corporate system) to measure the median size of this emulsion, its result is 55nm.
[modulation of ink]
(example VII A-1)
Utilize the method identical, obtained resin and formed admittedly and be divided into 50% polymer composition solution with resin emulsion A.Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes, add Cyanine Blue G-500pure-A (C.I.PB 15:1 then with the high speed dispersion device; Adret pigment Co., Ltd. system) 480.0 weight parts stirred 1 hour with the high speed dispersion device, had obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 10 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration., as the ink composition 1 of Table VII-3 shown in like that, with all kinds of SOLVENTS that contain resin emulsion A mix, made required ink for inkjet recording thereafter.
(example VII A-2)
Except substitutional crylic acid 50.4 weight parts, become methacrylic acid 13.2 weight parts, vinylformic acid 36.5 weight parts, and used resin emulsion is made as beyond the B, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 2 shown in the Table VII-3.
(example VII A-3)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 42.6 weight parts, and used resin is made as B30%, C70% (all is the weight substitution ratio in the resin emulsion, below identical) in addition, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 3 shown in the Table VII-3.
(example VII A-4)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 77.5 weight parts, used resin is made as beyond D50%, the E50%, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 4 shown in the Table VII-3.
(example VII A-5)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used Pigment Violet GC227-A (C.I.PY19; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, make the ink for inkjet recording of the composition example 9 shown in the Table VII-3 with embodiment 1.
(example VII A-6)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond Pigment Violet GC227-A 480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 10 shown in the Table VII-3 with embodiment 2.
(example VII A-7)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used FastYellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, make the ink for inkjet recording of the composition example 13 shown in the Table VII-4 with embodiment 1.
(example VII A-8)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond FastYellow 7413-A 480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 14 shown in the Table VII-4 with embodiment 2.
(example VII A-9)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch800 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 17 shown in the Table VII-4.
(example VII A-10)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond the Monarch800480.0 weight part, carry out in the same manner with embodiment 2, made the ink for inkjet recording of the composition example 18 shown in the Table VII-4.
(reference example VII-1)
Except employed resin emulsion being made as F, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 5 shown in the Table VII-3.
(reference example VII-2)
Except employed resin emulsion being made as G, carry out in the same manner with embodiment 3, made the ink for inkjet recording of the composition example 6 shown in the Table VII-3.
(reference example VII-3)
Except employed resin emulsion being made as G30%, H70%, carry out in the same manner with embodiment 4, made the ink for inkjet recording of the composition example 7 shown in the Table VII-3.
(reference example VII-4)
Except employed resin emulsion being made as I, carry out in the same manner with embodiment 2, made the ink for inkjet recording of the composition example 8 shown in the Table VII-3.
(reference example VII-5)
Except employed resin emulsion being made as F, carry out in the same manner with embodiment 5, made the ink for inkjet recording of the composition example 11 shown in the Table VII-4.
(reference example VII-6)
Except employed resin emulsion being made as F30%, G70%, carry out in the same manner with embodiment 6, made the ink for inkjet recording of the composition example 12 shown in the Table VII-4.
(reference example VII-7)
Except employed resin emulsion being made as F, carry out in the same manner with embodiment 7, made the ink for inkjet recording of the composition example 15 shown in the Table VII-4.
(reference example VII-8)
Except employed resin emulsion being made as F50%, G50%, carry out in the same manner with embodiment 8, made the ink for inkjet recording of the composition example 16 shown in the Table VII-4.
(reference example VII-9)
Except employed resin emulsion being made as F, carry out in the same manner with embodiment 9, made the ink for inkjet recording of the composition example 19 shown in the Table VII-4.
(reference example VII-10)
Except employed resin emulsion being made as I, carry out in the same manner with embodiment 10, made the ink for inkjet recording of the composition example 20 shown in the Table VII-4.
(evaluation test 1: the evaluation of common paper color emissivity)
The ink of example VII A-1～10 and reference example VII-1～10 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, (printing model is to have obtained the test body, print paper: common paper, print quality: hyperfine, color correct: do not have Print direction: two-way).After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag corporate system), (condition determination is light source: D50, field angle: 2 degree) to have measured OD of all kinds (Optical Density).With the result as the value representation of OD value in Table VII-1 and Table VII-2.
(evaluation test 2: the evaluation of glossiness)
With the ink of example VII A-1～10 and reference example VII-1～10 use ink-jet printer (EM-930C) at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), (printing model is to have obtained the test body, print paper: xerox and use paper, print quality: photo, color correct: do not have Print direction: two-way).20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).The results are shown in Table VII-1 and the Table VII-2.
(evaluation test 3: dispersed evaluation)
Utilize laser particle size analysis device (Zetasizer 3000, Malvern company) system) measure the median size of the particle in the ink of example VII A-1～10 and reference example VII-1～10.The results are shown in Table VII-1 and the Table VII-2.
(evaluation test 4: the evaluation of storage stability)
Utilize ink that rolling-ball viscometer (AMVn, Anton Paar corporate system) measured example VII A-1～10 and reference example VII-1～10 with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table VII-1 and Table VII-2.And, in Table VII-1 and the Table VII-2, give monomer composition, polymerization starter and pigment and ink for ink-jet print used in the manufacturing ink and form.
Figure BSA00000390083601141
Figure BSA00000390083601151
Figure BSA00000390083601161
Figure BSA00000390083601171
And the breviary symbol of expression is as follows in the Table VII-1～Table VII-4.
BZA: benzyl acrylate
AA: vinylformic acid
MAA: methacrylic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PV19:C.I. pigment violet 19 (quinoline a word used for translation ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
PBk7:C.I. Pigment black 7 (carbon black)
1,2-HD:1,2-hexylene glycol
TMP: TriMethylolPropane(TMP)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
BEPD:2-butyl-2-ethyl-1, ammediol
The result of record as can be known from Table VII-1～Table VII-4, under the situation of the ink for inkjet recording that has used example VII A-1～10, all good result in whole tests, yet under the situation of the ink for inkjet recording that has used reference example VII-1～10, in certain or a plurality of project of evaluation test, can't obtain good result.
[example VII A I]
(example VII A I-1)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carried out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution.Get the polymer composition solution that so obtains-part, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, weight-average molecular weight is 34000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes, add Cyanine BlueG-500pure-A (C.I.PB15:1 then with the high speed dispersion device; Adret pigment Co., Ltd. system) 480.0 weight parts stirred 1 hour with the high speed dispersion device, had obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.
Made ink for inkjet recording that ink Table VIII-3 shown in form example 1 thereafter.
(example VII A I-2)
Except substitutional crylic acid 50.4 weight parts, become beyond methacrylic acid 13.2 weight parts, vinylformic acid 36.5 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 2 shown in the Table VIII-3.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 60mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 32000.
(example VII A I-3)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 42.6 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 3 shown in the Table VIII-3.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 55mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 48000.
(example VII A I-4)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 77.5 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 4 shown in the Table VIII-3.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 100mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 29000.
(example VII A I-5)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 93.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 4 shown in the Table VIII-3.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 120mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 34000.
(example VII A I-6)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used Pigment Violet GC227-A (C.I.PV19; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet recording of the composition example 8 shown in the Table VIII-3 with embodiment 1.
(example VII A I-7)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond Pigment Violet GC227-A 480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 9 shown in the Table VIII-3 with embodiment 2.
(example VII A I-8)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond Pigment Violet GC227-A 480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 10 shown in the Table VIII-3 with embodiment 3.
(example VII A I-9)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond Pigment Violet GC227-A 480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 11 shown in the Table VIII-3 with embodiment 4.
(example VII A I-10)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used FastYellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, make the ink for inkjet recording of the composition example 14 shown in the Table VIII-4 with embodiment 1.
(example VII A I-11)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond FastYellow 7413-A 480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 15 shown in the Table VIII-4 with embodiment 2.
(example VII A I-12)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond FastYellow 7413-A 480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 16 shown in the Table VIII-4 with embodiment 3.
(example VII A I-13)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond FastYellow 7413-A 480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 17 shown in the Table VIII-4 with embodiment 4.
(example VII A I-14)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond FastYellow 7413-A 480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 18 shown in the Table VIII-4 with embodiment 5.
(example VII A I-15)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 21 shown in the Table VIII-4.
(example VII A I-16)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond Monarch 800480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 22 shown in the Table VIII-4 with embodiment 2.
(example VII A I-17)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond Monarch 800480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 23 shown in the Table VIII-4 with embodiment 3.
(example VII A I-18)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond Monarch 800480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 24 shown in the Table VIII-4 with embodiment 4.
(example VII A I-19)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond Monarch 800480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 25 shown in the Table VIII-4 with embodiment 5.
(reference example VIII-1)
Utilize the method identical, made the ink for inkjet recording of the composition example 6 shown in the Table VIII-3 with embodiment 2.
(reference example VIII-2)
Utilize the method identical, made the ink for inkjet recording of the composition example 7 shown in the Table VIII-3 with embodiment 5.
(reference example VIII-3)
Utilize the method identical, made the ink for inkjet recording of the composition example 12 shown in the Table VIII-3 with embodiment 6.
(reference example VIII-4)
Utilize the method identical, made the ink for inkjet recording of the composition example 13 shown in the Table VIII-3 with embodiment 8.
(reference example VIII-5)
Utilize the method identical, made the ink for inkjet recording of the composition example 19 shown in the Table VIII-4 with embodiment 10.
(reference example VIII-6)
Utilize the method identical, made the ink for inkjet recording of the composition example 20 shown in the Table VIII-4 with embodiment 14.
(reference example VIII-7)
Utilize the method identical, made the ink for inkjet recording of the composition example 26 shown in the Table VIII-4 with embodiment 15.
(reference example VIII-8)
Utilize the method identical, made the ink for inkjet recording of the composition example 27 shown in the Table VIII-4 with embodiment 17.
(evaluation test 1: the evaluation of common paper color emissivity)
The ink of example VII A I-1～19 and reference example VIII-1～8 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, (printing model is to have obtained the test body, print paper: common paper, print quality: hyperfine, color correct: do not have Print direction: two-way).After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag corporate system), (condition determination is light source: D50, field angle: 2 degree) to have measured OD of all kinds (Optical Density).With the result as the OD value representation in Table VIII-1 and Table VIII-2.
(evaluation test 2: the evaluation of glossiness)
With the ink of example VII A I-1～19 and reference example VIII-1～8 use ink-jet printer (EM-930C) at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), (printing model is to have obtained the test body, print paper: xerox and use paper, print quality: photo, color correct: do not have Print direction: two-way).20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).The results are shown in Table VIII-1 and the Table VIII-2.
(evaluation test 3: dispersed evaluation)
Utilize laser particle size analysis device (Zetasizer 3000, the Malvern corporate system) to measure the median size of the particle in the ink of example VII A I-1～19 and reference example VIII-1～8.The results are shown in Table VIII-1 and the Table VIII-2.
(evaluation test 4: the evaluation of storage stability)
Utilize ink that rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) measured example VII A I-1～19 and reference example VIII-1～8 with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table VIII-1 and Table VIII-2.And, in Table VIII-1 and the Table VIII-2, give used monomer composition, polymerization starter and used pigment in the manufacturing ink.
(evaluation test 5: the evaluation of ejection stability continuously)
The ink of example VII A I-1～19 and reference example VIII-1～8 is used ink-jet printer (EM-930C), on A4 version common paper, carry out 1000 printing on the spot continuously, try to achieve and not carry out the cleaning action ground mean value of the number of printing continuously, utilize following determinating reference to estimate.The results are shown in Table VIII-3 and the Table VIII-4.
Test method:
(1) in the printing, interrupts printing, carry out cleaning action and make it to restore in the stage that printing flaw (disorder of point, omission, bending) taking place.Under the situation that in recovery, needs repeatedly to clean, repeatedly cleaning action merged and regard flaw as 1 time.
(2) use up under the situation about temporarily stopping of the printing that causes at ink, or, do not count, promptly change print cartridge, begin printing once more judging significantly that reason is under the situation of the printing flaw that uses up of ink by print cartridge.
Judge: A ... the average number of printing continuously is more than 80
B ... the average number of printing continuously is more than 40
C ... the average number of printing continuously is more than 20
D ... the average number of printing continuously is below 20
(evaluation test 6: the evaluation of printing stability)
The ink of example VII A I-1～19 and reference example VIII-1～8 is used ink-jet printer (EM-930C), on A4 version common paper, use following printed patterns to carry out 3000 continuous printing, try to achieve and not carry out the cleaning action ground mean value of the number of printing continuously, utilize following determinating reference to estimate.The results are shown in Table VIII-3 and the Table VIII-4.
Printed patterns:
Disposed the pattern of half-angle English digital and mark literal randomly, make maximum possible that applying counts reaches print range apply to count about 12.5%.And the point of 360DPI (DPI=Dot per inch) usefulness has been used in the application point.
Test method:
(1) in the printing, interrupts printing, carry out cleaning action and make it to restore in the stage that printing flaw (disorder of point, omission, bending) taking place.Under the situation that in recovery, needs repeatedly to clean, repeatedly cleaning action merged and regard flaw as 1 time.
(2) use up under the situation about temporarily stopping of the printing that causes at ink, or, do not count, promptly change print cartridge, begin printing once more judging significantly that reason is under the situation of the printing flaw that uses up of ink by print cartridge.
Judge: A ... the average number of printing continuously is more than 600
B ... the average number of printing continuously is more than 300
C ... the average number of printing continuously is more than 150
D ... the average number of printing continuously is below 150
(evaluation test 7: the evaluation of printing quality (leaking profit))
The ink of example VII A I-1～19 and reference example VIII-1～8 is used ink-jet printer (EM-930C), at photo with paper＜gloss go up printing Green (Cyan+Yellow), Red (Magenta+Yellow), Blue (Cyan+Magenta) and Black distinguish adjacent image on the spot, utilize following determinating reference to estimate each adjacent (boundary) portion.The results are shown in Table VIII-3 and the Table VIII-4.
Judge: A ... interface is divided clear, and is very good
B ... interface is distinguished one from the other, and is good
C ... though interface is hard to tell Chu, be the practical no problem degree that
D ... boundary part messy (collapesed) can't be used for practicality
(evaluation test 8: the evaluation of stopping up Restoration)
The ink of example VII A I-1～19 and reference example VIII-1～8 is filled in the ink-jet printer (EM-930C), after having confirmed that the initial stage can normally spray, cut off the main body power supply, loaded under the state of print cartridge, be placed under the environment of 40 ℃ of 20%RH in maintenance.
After 2 months, take out printer, insert power supply after temperature is reduced to normal temperature by the time, watch whether normally ejection of ink.In addition, under situation about normally not spraying, clean restoring action, try to achieve the essential number of times in the time can normally spraying, utilize following determinating reference to estimate.The results are shown in Table VIII-3 and the Table VIII-4.
Judge: A ... at power supply is ON, or cleaning moving once in the time normally spray.
B ... when being 2～3 times, cleaning action normally sprays.
C ... when being 4～6 times, cleaning action normally sprays.
D ... even carry out 6 also not ejections normally of cleaning action.
Figure BSA00000390083601261
Figure BSA00000390083601271
Figure BSA00000390083601281
And the breviary symbol of expression is as follows in the Table VIII-1～Table VIII-4.
BZA: benzyl acrylate
AA: vinylformic acid
MAA: methacrylic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PV19:C.I. pigment violet 19 (quinoline a word used for translation ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
PBk7:C.I. Pigment black 7 (carbon black)
1,2-HD:1,2-hexylene glycol
4-m-1,2-PD:4-methyl isophthalic acid, 2-pentanediol
TEG: triglycol
DPG: dipropylene glycol
1,3-PD:1, ammediol
TMP: TriMethylolPropane(TMP)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
BEPD:2-butyl-2-ethyl-1, ammediol
The result of record as can be known from Table VIII-1～Table VIII-4, under the situation of the ink for inkjet recording that has used example VII A I-1～19, all good result in whole tests, yet under the situation of the ink for inkjet recording that has used reference example VIII-1～8, in certain or a plurality of project of evaluation test, can't obtain good result.
[example I X]
(manufacturing of dispersion 1)
Dispersion 1 has been used the U.S. Cabot corporate system Monarch880 as carbon black (PBk7).To possess whipping appts, thermometer, the reaction vessel interior of return line and dropping funnel with nitrogen replacement after, add vinylformic acid to 65 parts of cumyl phenoxy group glycol esters, 10 parts of benzyl acrylates, 2 parts in vinylformic acid, 0.3 part of t-lauryl mercaptan and be heated to 70 ℃, in dropping funnel, add the vinylformic acid of preparation in addition to 150 parts of cumyl phenoxy group glycol esters, 15 parts in vinylformic acid, 5 parts of butyl acrylates, 1 part of t-lauryl mercaptan, 1 part of the two isovaleronitrile of 20 parts of methyl ethyl ketones and azo make the dispersed polymeres polymerization reaction take place when dripping in reaction vessel with 4 hours.Then, in reaction vessel, add methyl ethyl ketone, made the dispersing polymer solution of 40% concentration.
In addition, with 40 parts of described dispersing polymer solutions with as 30 parts of Monarch880 powders (Cabot corporate system), 100 parts of the aqueous sodium hydroxide solutions of 0.1mol/L, 30 parts of mixing of methyl ethyl ketone of carbon black.Use ultra-high voltage homogenizer (Co., Ltd. Sugino Machine make UltimizerHJP-25005) with 200MPa carry out 8 and take turns dispersion thereafter.Afterwards, transfer in other container, add 300 parts of ion exchanged waters, stirred again 1 hour.After this, use rotatory evaporator that the part of the whole and water of methyl ethyl ketone is removed, be adjusted into pH8.5 with the sodium hydroxide neutralization of 0.1mol/L.Afterwards, filter, formed pigment concentration with the ion exchanged water adjustment and be 15% dispersion 1 with the film filter of 0.3 μ m.The mensuration of the weight-average molecular weight of dispersed polymeres is a part of getting dispersed polymeres, use the gel permeation chromatography (GPC) of system L7100 system of Hitachi Co., Ltd, surveys periodic vinylbenzene conversion molecular weight determination as solvent is made as THF.
(manufacturing of dispersion 2)
At first, dispersion 2 is to use pigment Blue 15: 1 (the trichlorine copper phthalocyanine: adret pigment Co., Ltd. makes G500) made in the same manner with dispersion 1.
(manufacturing of dispersion 3)
At first, dispersion 3 is to use pigment violet 19 (quinoline a word used for translation ketone pigment: the Clariant system) make in the same manner with dispersion 1.
(manufacturing of dispersion 4)
At first, dispersion 4 is to use Pigment Yellow 73 74 (condensed azo-pigment: the Clariant system) make in the same manner with dispersion 1.
(the ink-jet modulation example of paint ink)
Below, will be suitable for ink-jet and be shown among the Table I X-2 with the example of the composition of paint ink.Form ink-jet of the present invention and be to use each dispersion of making, make by mixing with the vehicles composition of composition beyond the described dispersion liquid of conduct shown in the Table I X-2 with described method with the adjustment of paint ink.And, used in the water of the residual amount in Table I X-1 and in ion exchanged water, added the 0.05% corrosive Topside 240 (PermachemAsia corporate system) that is used for preventing ink, 0.02% the corrosive benzotriazole that is used to prevent the ink gun member, 0.04% the water of EDTA (ethylenediamine tetraacetic acid (EDTA)) 2Na salt of influence of metal ion that is used to reduce ink system respectively.
(example I X-1)
Made ink 1 by using dispersion 1 to mix with the vehicles composition shown in the Table I X-2.
(example I X-2)
Made ink 2 by using dispersion 2 to mix with the vehicles composition shown in the Table I X-2.
(example I X-3)
Made ink 3 by using dispersion 3 to mix with the vehicles composition shown in the Table I X-2.
(example I X-4)
Made ink 4 by using dispersion 4 to mix with the vehicles composition shown in the Table I X-2.
(reference example IX-1)
Identical with dispersion 1, use is as the U.S. Cabot corporate system Monarch880 of carbon black (PBk7), vinylformic acid amount when making polymkeric substance used in the dispersion except reducing, use is made as acid number beyond 40 the polymkeric substance, make pigment dispersion 5 in the same manner with embodiment 1, made ink 5 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 1.
(reference example IX-2)
Identical with dispersion 1, use is as the U.S. Cabot corporate system Monarch880 of carbon black (PBk7), vinylformic acid amount when making polymkeric substance used in the dispersion except increasing, use is made as acid number beyond 200 the polymkeric substance, make pigment dispersion 6 in the same manner with embodiment 1, made ink 6 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 1.
(reference example IX-3)
Identical with reference example 1, use pigment Blue 15: 1 (trichlorine copper phthalocyanine: the system G500 of adret pigment Co., Ltd.), vinylformic acid amount when making polymkeric substance used in the dispersion except reducing, use is made as acid number beyond 40 the polymkeric substance, make pigment dispersion 7 in the same manner with embodiment 2, made ink 7 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-4)
Identical with reference example 2, use pigment Blue 15: 1 (trichlorine copper phthalocyanine: the system G500 of adret pigment Co., Ltd.), vinylformic acid amount when making polymkeric substance used in the dispersion except increasing, use is made as acid number beyond 200 the polymkeric substance, make pigment dispersion 8 in the same manner with embodiment 2, made ink 8 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-5)
Identical with reference example 1, use pigment violet 19 (quinoline a word used for translation ketone pigment: the Clariant system), vinylformic acid amount when making polymkeric substance used in the dispersion except reducing, use is made as acid number beyond 40 the polymkeric substance, make pigment dispersion 9 in the same manner with embodiment 3, made ink 9 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-6)
Identical with reference example 2, use pigment violet 19 (quinoline a word used for translation ketone pigment: the Clariant system), vinylformic acid amount when making polymkeric substance used in the dispersion except increasing, use is made as acid number beyond 200 the polymkeric substance, make pigment dispersion 10 in the same manner with embodiment 3, made ink 10 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-7)
Identical with reference example 1, use Pigment Yellow 73 74 (condensed azo-pigment: the Clariant system), vinylformic acid amount when making polymkeric substance used in the dispersion except reducing, use is made as acid number beyond 40 the polymkeric substance, make pigment dispersion 11 in the same manner with embodiment 4, made ink 11 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-8)
Identical with reference example 2, use Pigment Yellow 73 74 (condensed azo-pigment: the Clariant system), vinylformic acid amount when making polymkeric substance used in the dispersion except increasing, use is made as acid number beyond 200 the polymkeric substance, make pigment dispersion 12 in the same manner with embodiment 4, made ink 12 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-9)
Identical with dispersion 1, use is as the U.S. Cabot corporate system Monarch880 of carbon black (PBk7), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except increasing, use is made as the weight-average molecular weight of polymkeric substance beyond 15000 the polymkeric substance, make pigment dispersion 13 in the same manner with embodiment 1, made ink 13 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 1.
(reference example IX-10)
Identical with dispersion 1, use is as the U.S. Cabot corporate system Monarch880 of carbon black (PBk7), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except reducing, use is made as the weight-average molecular weight of polymkeric substance beyond 110000 the polymkeric substance, make pigment dispersion 14 in the same manner with embodiment 1, made ink 14 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 1.
(reference example IX-11)
Identical with reference example 1, use pigment Blue 15: 1 (trichlorine copper phthalocyanine: the system G500 of adret pigment Co., Ltd.), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except increasing, use is made as the weight-average molecular weight of polymkeric substance beyond 15000 the polymkeric substance, make pigment dispersion 15 in the same manner with embodiment 2, made ink 15 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-12)
Identical with reference example 2, use pigment Blue 15: 1 (trichlorine copper phthalocyanine: the system G500 of adret pigment Co., Ltd.), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except reducing, use is made as the weight-average molecular weight of polymkeric substance beyond 110000 the polymkeric substance, make pigment dispersion 16 in the same manner with embodiment 2, made ink 16 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-13)
Identical with reference example 1, use pigment violet 19 (quinoline a word used for translation ketone pigment: the Clariant system), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except increasing, use is made as the weight-average molecular weight of polymkeric substance beyond 15000 the polymkeric substance, make pigment dispersion 17 in the same manner with embodiment 3, made ink 17 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-14)
Identical with reference example 2, use pigment violet 19 (quinoline a word used for translation ketone pigment: the Clariant system), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except reducing, use is made as the weight-average molecular weight of polymkeric substance beyond 110000 the polymkeric substance, make pigment dispersion 18 in the same manner with embodiment 3, made ink 18 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-15)
Identical with reference example 1, use Pigment Yellow 73 74 (condensed azo-pigment: the Clariant system), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except increasing, use is made as the weight-average molecular weight of polymkeric substance beyond 15000 the polymkeric substance, make pigment dispersion 19 in the same manner with embodiment 4, made ink 19 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-16)
Identical with reference example 2, use Pigment Yellow 73 74 (condensed azo-pigment: the Clariant system), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except reducing, use is made as the weight-average molecular weight of polymkeric substance beyond 110000 the polymkeric substance, make pigment dispersion 20 in the same manner with embodiment 4, made ink 20 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 2.
(reference example IX-17)
Identical with dispersion 1, use is as the U.S. Cabot corporate system Monarch880 of carbon black (PBk7), changed dispersive pressure except using the polymkeric substance identical and taken turns the number with dispersion 1, make pigment dispersion 21～26 in the same manner with embodiment 1, made ink 21～26 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 1.
(reference example IX-18)
Identical with dispersion 2, use pigment Blue 15: 1 (trichlorine copper phthalocyanine: the system G500 of adret pigment Co., Ltd.), changed dispersive pressure except using the polymkeric substance identical and taken turns the number with dispersion 2, make pigment dispersion 27～32 in the same manner with embodiment 2, made ink 27～32 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 1.
(reference example IX-19)
Identical with dispersion 3, use pigment violet 19 (quinoline a word used for translation ketone pigment: the Clariant system), changed dispersive pressure except using the polymkeric substance identical and taken turns the number with dispersion 3, make pigment dispersion 33～38 in the same manner with embodiment 1, made ink 33～38 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 3.
(reference example IX-20)
Identical with dispersion 4, use Pigment Yellow 73 74 (condensed azo-pigment: the Clariant system), changed dispersive pressure except using the polymkeric substance identical and taken turns the number with dispersion 4, make pigment dispersion 39～44 in the same manner with embodiment 4, made ink 39～44 by mixing with the vehicles composition shown in the Table I X-2 in the same manner with embodiment 4.
(evaluation of dispersion stabilization)
Viscosity velocity of variation (%) and rate of descent (%) when the 60 ℃ of ink-jets that will use different dispersion of processing pressure and the different dispersion of wheel number to make have down been placed 30 days with paint ink are shown among the Table I X-1.Viscosity velocity of variation (%) expression when the dispersion stabilization conduct has been placed 30 days with each water-base ink under 60 ℃.Viscosity changes utilizes German Anton Paar system AMVn to measure down for 60 ° in angle, as percentage (%) expression of 1-(values after 30 days)/(value at initial stage).
(evaluation of common paper OD and glossy paper glossiness)
Used U.S. Xerox corporate system Xerox4024 paper as common paper, used Seiko Epson Corp's system photo paper＜gloss〉as glossy paper.Printer has used the ink-jet printer EM930C of Seiko Epson Corp's system, for common paper, use is estimated with the sample of the printing mode printing of the photographic printing quality of 720dpi, for glossy paper, use is estimated with the sample of the printing mode printing of the photographic printing quality of 1440dpi.The mensuration of OD is to use U.S. GRETAG corporate system GRETAG MACBETH SPECTROSCAN SPM-50 to carry out.The mensuration of glossiness is to make system gloss tester (gloss checker) IG-320 of Co., Ltd. of institute with the hole field mirror surface luster of the record surface of input angle 60 degree is measured, and each recording paper is got 5 times mean value.For medium, be Seiko Epson Corp's system photo paper＜gloss 〉, for printer, use the photographic printing quality printing of the system EM930C of Seiko Epson Corp with 720dpi.The results are shown among the Table I X-1.
(mensuration of ejection stability)
Use the system PX-V600 of Seiko Epson Corp as ink-jet printer, under 35 ℃ of 35% atmosphere, on the Xerox of Fuji corporate system XeroxP paper A4 version, utilize the Word of Microsoft with 100 pages of the ratio printings of the standard of character size 11, MSP Gothic, 4000 word/pages or leaves, estimate.The disorderly AA that is evaluated as will do not printed fully, to have a position the printing disorder be evaluated as A, to have 2～3 positions the printing disorder be evaluated as B, to have 4～5 positions the printing disorder be evaluated as C, the D that is evaluated as of the above printing disorder in 6 positions will be arranged, the results are shown among the Table I X-1.
Table I X-1
The result of the dispersion stabilization of embodiment 1, common paper OD, glossy paper glossiness and ejection stability
Figure BSA00000390083601371
Pressure: dispersive pressure (MPa), wheel: the wheel number, Mw: weight-average molecular weight,
Stability: storage stability, OD:OD value, gloss: glossy paper glossiness, ejection: ejection stability
Table I X-2
Each ink is formed (weight %)
Pigment P?B?k?7 P?B?15:1 P?V?19 P?Y?74
Embodiment 1, reference example 1,2,9,10,17 46.7 - - -
Embodiment 2, reference example 3,4,11,12,18 - 33.3 - -
Embodiment 3, reference example 5,6,13,14,19 - - 40 -
Embodiment 4, reference example 7,8,15,16,20 - - - 40
?TEGmBE 2 1 1 1
1, the 2-hexylene glycol 3 4 4 4
Glycerine 10 15 10 10
TriMethylolPropane(TMP) 4 7 5 5
?Surfinol?104 0.15 0.15 0.15 0.15
Ion exchanged water Residual amount Residual amount Residual amount Residual amount
PBk7:C.I. Pigment black 7
PB15:1:C.I. pigment Blue 15: 1
PV19:C.I. pigment violet 19
PY74:C.I. Pigment Yellow 73 74
TEGmBE: triglycol single-butyl ether
Surfinol 104: day letter chemistry system alkynes class glycols tensio-active agent
[embodiment X]
(embodiment X-1)
With Cyanine Blue G-500pure-A (C.I.PB15:1; Adret pigment Co., Ltd. system) 500 weight parts are mixed in tetramethylene sulfone 950 weight parts, add thionamic acid 25 weight parts, stir under 140～150 ℃ 4 hours.The slip of gained is dropped in ion exchanged water 3000 weight parts, with 12000rpm utilize separating centrifuge obtain surface treatment wet cake.With the wet cake redispersion in the ion exchanged water of 6000 weight parts of this pigment, utilize ultra-filtration with pigment concentration simmer down to 25 weight %.This aqueous pigment dispersions demonstrates the slightly acidic of pH4.5～5.5.
(embodiment X-2)
Monarch 800 (C.I.PBk7:Cabot system) 500 weight parts are mixed in tetramethylene sulfone 950 weight parts, add thionamic acid 25 weight parts, under 140～150 ℃, stirred 8 hours.The slip of gained is dropped in ion exchanged water 3000 weight parts, with 12000rpm utilize separating centrifuge obtain surface treatment wet cake.With the wet cake redispersion in the ion exchanged water of 6000 weight parts of this pigment, utilize ultra-filtration with pigment concentration simmer down to 25 weight %.This aqueous pigment dispersions demonstrates the slightly acidic of pH4.5～5.5.
(embodiment X-3)
Pigment Violet GC227-A 500 weight parts are mixed in tetramethylene sulfone 1500 weight parts, add thionamic acid 25 weight parts, under 140～150 ℃, stirred 4 hours.The slip of gained is dropped in ion exchanged water 3000 weight parts, with 12000rpm utilize separating centrifuge obtain surface treatment wet cake.With the wet cake redispersion in the ion exchanged water of 6000 weight parts of this pigment, utilize ultra-filtration with pigment concentration simmer down to 25 weight %.This aqueous pigment dispersions demonstrates the slightly acidic of pH4.5～5.5.
(embodiment X-4)
With Fast Yellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) 500 weight parts are mixed in tetramethylene sulfone 1200 weight parts, add thionamic acid 25 weight parts, stir under 140～150 ℃ 4 hours.The slip of gained is dropped in ion exchanged water 3000 weight parts, with 12000rpm utilize separating centrifuge obtain surface treatment wet cake.With the wet cake redispersion in the ion exchanged water of 6000 weight parts of this pigment, utilize ultra-filtration with pigment concentration simmer down to 25 weight %.This aqueous pigment dispersions demonstrates the slightly acidic of pH4.5～5.5.
(embodiment X-5)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carry out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtain resin and form admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 50mgKOH/g, and weight-average molecular weight is 22000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes with the high speed dispersion device, then add synthetic Cyan surface treated pigments 480.0 weight parts among the embodiment 1, stirred 1 hour with the high speed dispersion device, obtain the colo(u)rant dispersion slip.After this, utilize ultra-high voltage dispersion machine (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.Make ink for inkjet that ink Table X-2 shown in form routine A thereafter.
(embodiment X-6)
Be made as 85.3 weight parts except substitutional crylic acid 38.8 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 8.2 weight parts, carry out in the same manner with embodiment 5, make the ink for inkjet of the composition example A shown in the Table X-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 110mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(embodiment X-7)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 77.5 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.88 weight parts, carry out in the same manner with embodiment 5, make the ink for inkjet of the composition example A shown in the Table X-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 50mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(embodiment X-8)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 170.5 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.91 weight parts, carry out in the same manner with embodiment 1, make the ink for inkjet of the composition example A shown in the Table X-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 110mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(embodiment X-9)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Black surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 2 and used, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example B shown in the Table X-2.
(embodiment X-10)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Black surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 2 and used, carry out in the same manner with embodiment 6, made the ink for inkjet of the composition example B shown in the Table X-2.
(embodiment X-11)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Black surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 2 and used, carry out in the same manner with embodiment 7, made the ink for inkjet of the composition example B shown in the Table X-2.
(embodiment X-12)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Black surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 2 and used, carry out in the same manner with embodiment 8, made the ink for inkjet of the composition example B shown in the Table X-2.
(embodiment X-13)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Magenta surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 3 and used, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example C shown in the Table X-2.
(embodiment X-14)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Magenta surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 3 and used, carry out in the same manner with embodiment 6, made the ink for inkjet of the composition example C shown in the Table X-2.
(embodiment X-15)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Magenta surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 3 and used, carry out in the same manner with embodiment 7, made the ink for inkjet of the composition example C shown in the Table X-2.
(embodiment X-16)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Magenta surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 3 and used, carry out in the same manner with embodiment 8, made the ink for inkjet of the composition example C shown in the Table X-2.
(embodiment X-17)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Yellow surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 4 and used, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example D shown in the Table X-2.
(embodiment X-18)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Yellow surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 4 and used, carry out in the same manner with embodiment 6, made the ink for inkjet of the composition example D shown in the Table X-2.
(embodiment X-19)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Yellow surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 4 and used, carry out in the same manner with embodiment 7, made the ink for inkjet of the composition example D shown in the Table X-2.
(embodiment X-20)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Yellow surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 4 and used, carry out in the same manner with embodiment 8, made the ink for inkjet of the composition example D shown in the Table X-2.
(reference example X-1)
Be made as 31.0 weight parts except substitutional crylic acid 38.8 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 7.1 weight parts, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example A shown in the Table X-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 40mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(reference example X-2)
Be made as 100.8 weight parts except substitutional crylic acid 38.8 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 8.8 weight parts, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example A shown in the Table X-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 130mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(reference example X-3)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 62.0 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.87 weight parts, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example A shown in the Table X-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 40mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(reference example X-4)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 201.5 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.92 weight parts, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example A shown in the Table X-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 130mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(reference example X-5)
Synthetic aqueous pigment dispersions among the embodiment 1 is diluted with ion exchanged water, make pigment concentration reach 25 weight %, made the ink for inkjet of the composition example A shown in the Table X-2 to 15 weight %.
(reference example X-6)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts, and be made as beyond t-butylperoxy (2-ethylhexanoate) 7.9 weight parts, carry out in the same manner, make the ink for inkjet of the composition example A shown in the Table X-2 with embodiment 5.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 50mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 18000.
(reference example X-7)
Be made as 85.3 weight parts except substitutional crylic acid 38.8 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 8.6 weight parts, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example A shown in the Table X-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 110mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 18000.
(reference example X-8)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 77.5 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.86 weight parts, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example A shown in the Table X-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 50mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 130000.
(reference example X-9)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 170.5 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.89 weight parts, carry out in the same manner with embodiment 5, made the ink for inkjet of the composition example A shown in the Table X-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 110mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 130000.
(reference example X-10)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Black surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 2 and used, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example B shown in the Table X-2.
(reference example X-11)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Black surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 2 and used, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example B shown in the Table X-2.
(reference example X-12)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Black surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 2 and used, carry out in the same manner with reference example 3, made the ink for inkjet of the composition example B shown in the Table X-2.
(reference example X-13)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Black surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 2 and used, carry out in the same manner with reference example 4, made the ink for inkjet of the composition example B shown in the Table X-2.
(reference example X-14)
Synthetic aqueous pigment dispersions among the embodiment 2 is diluted with ion exchanged water, make pigment concentration reach 25 weight %, made the ink for inkjet of the composition example B shown in the Table X-2 to 15 weight %.
(reference example X-15)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Magenta surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 3 and used, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example C shown in the Table X-2.
(reference example X-16)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Magenta surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 3 and used, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example C shown in the Table X-2.
(reference example X-17)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Magenta surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 3 and used, carry out in the same manner with reference example 3, made the ink for inkjet of the composition example C shown in the Table X-2.
(reference example X-18)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Magenta surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 3 and used, carry out in the same manner with reference example 4, made the ink for inkjet of the composition example C shown in the Table X-2.
(reference example X-19)
Synthetic aqueous pigment dispersions among the embodiment 3 is diluted with ion exchanged water, make pigment concentration reach 25 weight %, made the ink for inkjet of the composition example C shown in the Table X-2 to 15 weight %.
(reference example X-20)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Yellow surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 4 and used, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example D shown in the Table X-2.
(reference example X-21)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Yellow surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 4 and used, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example D shown in the Table X-2.
(reference example X-22)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Yellow surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 4 and used, carry out in the same manner with reference example 3, made the ink for inkjet of the composition example D shown in the Table X-2.
(reference example X-23)
Except replacing synthetic Cyan surface treated pigments dispersion 480.0 weight parts among the embodiment 1, synthetic pigment concentration is beyond Yellow surface treated pigments dispersion 480.0 weight parts of 25 weight % among the embodiment 4 and used, carry out in the same manner with reference example 4, made the ink for inkjet of the composition example D shown in the Table X-2.
(reference example X-24)
Synthetic aqueous pigment dispersions among the embodiment 1 is diluted with ion exchanged water, make pigment concentration reach 25 weight %, made the ink for inkjet of the composition example D shown in the Table X-2 to 15 weight %.
(evaluation test 1: the evaluation method of common paper color emissivity)
The ink for ink-jet print of embodiment X-1～20 and reference example X-1～24 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, obtain testing body.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag company (U.S.) system), measure OD value of all kinds.The result as the value representation of OD value in Table X-1.
(evaluation test 2: the evaluation method of glossiness)
The ink for ink-jet print of embodiment X-1～20 and reference example X-1～24 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).Its result is shown in the Table X-1.
(evaluation test 3: dispersed evaluation method)
Utilize laser particle size analysis device (Zetasizer 3000, Malvern company (Britain) system) to measure the median size of the particle in the ink for ink-jet print of embodiment X-1～20 and reference example X-1～24.Its result is shown in the Table X-1.
(evaluation test 4: the evaluation method of storage stability)
Utilize rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) to measure ink for ink-jet print used in embodiment X-1～20 and reference example X-1～24 with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table X-1.And, in the Table X-1, give monomer composition, polymerization starter and pigment and ink for ink-jet print used in the manufacturing ink for ink-jet print and form.
Table X-1
Table X-2
Figure BSA00000390083601501
And the breviary symbol of expression is as follows in the Table X-1～Table X-2.
BZA: benzyl acrylate
AA: vinylformic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
PBk7:C.I. Pigment black 7 (carbon black)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PV19:C.I. pigment violet 19 (quinoline a word used for translation ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
BEPD:2-butyl-2-ethyl-1, ammediol
1,2-HD:1,2-hexylene glycol
TMP: TriMethylolPropane(TMP)
EDTA: disodium ethylene diamine tetraacetate
From the result of Table X-1 and Table X-2 as can be known, under the situation of the ink for ink-jet print that has used embodiment X-1～20, evaluation test 1～5 all is good result, yet under the situation of the ink for ink-jet print that has used reference example X-1～24, in certain or a plurality of project of evaluation test 1～5, or not good result.
[embodiment XI]
(making of composition for ink)
(implementing ink example 1)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, vinylformic acid 50.4 amounts part and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carry out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes, add Cyanine BlueG-500pure-A (C.I.PB15:1 then with the high speed dispersion device; Adret pigment Co., Ltd. system) 480.0 weight parts stirred 1 hour with the high speed dispersion device, had obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.
Make the ink for inkjet recording of the composition example 1 shown in the Table X I-2 thereafter.
(implementing ink example 2)
Except substitutional crylic acid 50.4 weight parts, become beyond methacrylic acid 13.2 weight parts, vinylformic acid 36.5 weight parts, carry out in the same manner with composition example 1, made the ink for inkjet recording of the composition example 2 shown in the Table X I-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 60mgKOH/g, and weight-average molecular weight is 32000.
(implementing ink example 3)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 42.6 weight parts, carry out in the same manner with composition example 1, made the ink for inkjet recording of the composition example 3 shown in the Table X I-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 55mgKOH/g, and weight-average molecular weight is 48000.
(implementing ink example 4)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 77.5 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 4 shown in the Table X I-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 100mgKOH/g, and weight-average molecular weight is 29000.
(implementing ink example 5)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used Pigment Violet GC227-A (C.I.PV19; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet recording of the composition example 5 shown in the Table X I-2 with composition example 1.
(implementing ink example 6)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond Pigment Violet GC227-A 480.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 6 shown in the Table X I-2 with composition example 2.
(implementing ink example 7)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used FastYellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, make the ink for inkjet recording of the composition example 7 shown in the Table X I-2 with composition example 1.
(implementing ink example 8)
Except replacement Cyanine Blue G-500pure-A 480.0 weight parts, and used beyond the FastYellow 7413-A480.0 weight part, carried out in the same manner, made the ink for inkjet recording of the composition example 8 shown in the Table X I-2 with composition example 2.
(reference inks example 1)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 116.3 weight parts, carry out in the same manner with composition example 1, made the ink for inkjet recording of the composition example 9 shown in the Table X I-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 150mgKOH/g, and weight-average molecular weight is 34000.
(reference inks example 2)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 100.8 weight parts, carry out in the same manner with composition example 5, made the ink for inkjet recording of the composition example 10 shown in the Table X I-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 130mgKOH/g, and weight-average molecular weight is 29000.
(reference inks example 3)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 100.8 weight parts, carry out in the same manner with composition example 7, made the ink for inkjet recording of the composition example 11 shown in the Table X I-2.
(evaluation test 1: the evaluation of common paper color emissivity)
The ink of implementing ink example 1～8 and reference inks example 1～3 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, (printing model is to have obtained the test body, print paper: common paper, print quality: hyperfine, color correct: do not have Print direction: two-way).After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag corporate system), (condition determination is light source: D50, field angle: 2 degree) to have measured OD of all kinds (Optical Density).With the result as the OD value representation in Table X I-1.
(evaluation test 2: the evaluation of glossiness)
The ink of implementing ink example 1～8 and reference inks example 1～3 is used ink-jet printer (EM-930C), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), (printing model is to have obtained the test body, print paper: xerox and use paper, print quality: photo, color correct: do not have Print direction: two-way).20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).The results are shown among the Table X I-1.
(evaluation test 3: dispersed evaluation)
Utilize laser particle size analysis device (Zetasizer 3000, the Malvern corporate system) to measure the median size of particle in the ink of implementing ink example 1～8 and reference inks example 1～3.The results are shown among the Table X I-1.
(evaluation test 4: the evaluation of storage stability)
The ink that utilizes rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) to measure to implement ink example 1～8 and reference inks example 1～3 is with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table X I-1.And, among the Table X I-1, give used monomer composition, polymerization starter and used pigment in the manufacturing ink.
Table X I-1
Figure BSA00000390083601551
And the breviary symbol of representing among Table X I-1～Table X I-2 is as follows.
BZA: benzyl acrylate
AA: vinylformic acid
MAA: methacrylic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PV19:C.I. pigment violet 19 (quinoline a word used for translation ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
BEPD:2-butyl-2-ethyl-1, ammediol
1,2-HD:1,2-hexylene glycol
TMP: TriMethylolPropane(TMP)
(embodiment XI-1～4, reference example XI-1～6)
Utilize the combination of putting down in writing among the Table X I-3, make the ink group of embodiment 1～4 and reference example 1～6, the ink-jet printer of being put down in writing below using, (printing model is at XeroxP paper, print paper: common paper, print quality: hyperfine, color correct: do not have) and photo with paper＜gloss (printing model is, print paper: photo paper＜gloss 〉, print quality: photo, color correct: do not have) on, mixes applying cyan, magenta, yellow three kinds of colors and form black, obtained the test of the image on the spot body of black.
(recording unit classification)
(1) printer: PX-V600 (Seiko Epson Corp's system)
Nozzle arrangement: vertical
Apply order: according to the color sequences of putting down in writing among the Table X I-3, the order with the first → the second → the 3rd applies
Print direction: two-way
(2) printer: PX-A550 (Seiko Epson Corp's system)
Nozzle arrangement: horizontal stroke
Apply order: according to the color sequences of putting down in writing among the Table X I-3, the order with the first → the second → the 3rd applies
Print direction: outlet
(3) printer: PX-A550 (Seiko Epson Corp's system)
Nozzle arrangement: horizontal stroke
Apply order: according to the color sequences of putting down in writing among the Table X I-3, the order with the three → the second → the first applies
Print direction: loop
For the printing process of the ink group of embodiment XI-1～4 and reference example XI-1～6,, put down in writing the value of described (1)～(3) as the recording unit classification of putting down in writing among the Table X I-3.
(evaluation test 5: the color emissivity evaluation of black part)
The test body that combination that utilize to implement ink example 1～8 and reference inks example 1～3 is obtained uses GRETAGMACBETH SPECTROSCAN SP50 (Gretag corporate system) to measure OD of all kinds (Optical Density), and (condition determination is, light source: D50, field angle: 2 degree).With the result as the OD value representation in Table X I-3.
(evaluation test 6: the glossiness evaluation of black part)
In the middle of the test body that obtains for combination that utilize to implement ink example 1～8 and reference inks example 1～3 by the formed test body of EPSON photo, measured 20 of this test body with glossmeter (HG-268, Suga trier Co., Ltd. system) and spent gloss.The results are shown among the Table X I-3.
Table X I-3
The result who puts down in writing from Table X I-1 and Table X I-3 as can be known, under the situation of having used the ink jet recording method of implementing ink example 1～8, all good result in whole tests, yet if the ink for inkjet recording of reference inks example 1～3, in certain or a plurality of project of evaluation test, can't obtain good result.
[embodiment XII]
(embodiment XII-1)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, vinylformic acid 50.4 amounts part and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carried out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes, add PALIOTOLYellow D0960 (C.I. pigment yellow 13 8 then with the high speed dispersion device; BASF AG's system) 480.0 weight parts stirred 1 hour with the high speed dispersion device, had obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.Make ink for inkjet recording that ink Table X II-3 shown in form example 1 thereafter.
(embodiment XII-2)
Except substitutional crylic acid 50.4 weight parts, become beyond methacrylic acid 13.2 weight parts, vinylformic acid 36.5 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 2 shown in the Table X II-3.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 60mgKOH/g, and weight-average molecular weight is 32000.
(embodiment XII-3)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 42.6 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 3 shown in the Table X II-3.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 55mgKOH/g, and weight-average molecular weight is 48000.
(embodiment XII-4)
Except replacing PALIOTOL Yellow D0960480.0 weight part, become PALIOTOLYellow D0960456.0 weight part, Fast Yellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 24.0 weight parts, carries out in the same manner, make the ink for inkjet recording of the composition example 4 shown in the Table X II-3 with embodiment 1.
(embodiment XII-5)
Except replacing PALIOTOL Yellow D0960480.0 weight part, become beyond PALIOTOLYellow D0960320.0 weight part, Fast Yellow 7413-A 160.0 weight parts, carry out in the same manner with embodiment 1, make the ink for inkjet recording of the composition example 5 shown in the Table X II-3.
(embodiment XII-6)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 77.5 weight parts, replace PALIOTOL Yellow D0960480.0 weight part, become beyond PALIOTOL Yellow D096048.0 weight part, the Fast Yellow 7413-A432.0 weight part, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 6 shown in the Table X II-3.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 100mgKOH/g, and weight-average molecular weight is 29000.
(embodiment XII-7)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 93.0 weight parts, replace PALIOTOL Yellow D0960480.0 weight part, become beyond PALIOTOL Yellow D096030.0 weight part, the Fast Yellow 7413-A450.0 weight part, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 7 shown in the Table X II-3.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 120mgKOH/g, and weight-average molecular weight is 34000.
(reference example XII-1)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 100.8 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 8 shown in the Table X II-4.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 130mgKOH/g, and weight-average molecular weight is 29000.
(reference example XII-2)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 116.3 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 9 shown in the Table X II-4.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 150mgKOH/g, and weight-average molecular weight is 34000.
(reference example XII-3)
Except substitutional crylic acid 42.6 weight parts, become beyond vinylformic acid 155.0 weight parts, carry out in the same manner with embodiment 3, made the ink for inkjet recording of the composition example 10 shown in the Table X II-4.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number 200mgKOH/g of the solid substance of the polymer composition of gained, weight-average molecular weight is 29000.
(reference example XII-4)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 19.2 weight parts, carry out in the same manner with embodiment 4, made the ink for inkjet recording of the composition example 11 shown in the Table X II-4.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 10000.
(reference example XII-5)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 14.2 weight parts, carry out in the same manner with embodiment 5, made the ink for inkjet recording of the composition example 12 shown in the Table X II-4.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 60mgKOH/g, and weight-average molecular weight is 18000.
(reference example XII-6)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 2.3 weight parts, carry out in the same manner with embodiment 6, made the ink for inkjet recording of the composition example 13 shown in the Table X II-4.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 14000.
(reference example XII-7)
Except substitutional crylic acid 93.0 weight parts, become beyond vinylformic acid 23.3 weight parts, carry out in the same manner with embodiment 7, made the ink for inkjet recording of the composition example 14 shown in the Table X II-4.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 30mgKOH/g, and weight-average molecular weight is 33000.
(evaluation test 1: the evaluation of common paper color emissivity)
The ink of embodiment XII-1～7 and reference example XII-1～7 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, (printing model is to have obtained the test body, print paper: common paper, print quality: hyperfine, color correct: do not have Print direction: two-way).After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag corporate system), (condition determination is light source: D50, field angle: 2 degree) to have measured OD of all kinds (Optical Density).With the result as the OD value representation in Table X II-1 and Table X II-2.
(evaluation test 2: the evaluation of glossiness)
The ink of embodiment XII-1～7 and reference example XII-1～7 is used ink-jet printer (EM-930C), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), (printing model is to have obtained the test body, print paper: xerox and use paper, print quality: photo, color correct: do not have Print direction: two-way).20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).The results are shown among Table X II-1 and the Table X II-2.
(evaluation test 3: dispersed evaluation)
Utilize laser particle size analysis device (Zetasizer 3000, the Malvern corporate system) to measure the median size of particle in the ink of embodiment XII-1～7 and reference example XII-1～7.The results are shown among Table X II-1 and the Table X II-2.
(evaluation test 4: the evaluation of storage stability)
Utilize ink that rolling-ball viscometer (AMVn, Anton Paar corporate system) measured embodiment XII-1～7 and reference example XII-1～7 with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mpas)/initial stage viscosity (mpas) after 1 week under 70 ℃ is in Table X II-1 and Table X II-2.And, among Table X II-1 and the Table X II-2, give monomer composition, polymerization starter and pigment and ink used in the manufacturing ink and form.
(evaluation test 5: sunproof evaluation)
With the ink of embodiment XII-1～7 and reference example XII-1～7 with ink-jet printer (EM-930C) at photo with paper＜gloss on print on the spot, adjustment applies load, make it to fall into the scope of OD (Optical Density)=0.9～1.1, (printing model is to have obtained the test body, print paper: xerox and use paper, print quality: photo, color correct: do not have Print direction: two-way).With these test bodies normal temperature is indoor placed 3 days after, use xenon lamp weather resistance test machine (XL-75S; Suga trier Co., Ltd. system), at 24 ℃ of 60%RH; BPT (black panel temperature) is 40 ℃; The illumination of illumination wavelength zone 300～400nm is 34W/m 2Condition under, the light that has carried out 720 hours expose to be handled.
Expose the test body of handling front and back for described light, use GRETAGMACBETHSPECROSCAN SP50 to measure OD, utilize following formula to try to achieve optical concentration survival rate (ROD).The results are shown among Table X II-3 and the Table X II-4.
ROD(％)＝(D/D 0)×100
D: light exposes the OD after handling
D 0: light exposes the OD before handling
Table X II-1
Figure BSA00000390083601651
Table X II-2
Figure BSA00000390083601652
Table X II-3
Figure BSA00000390083601661
Table X II-4
And the breviary symbol of representing among Table X II-1～Table X II-4 is as follows.
BZA: benzyl acrylate
AA: vinylformic acid
MAA: methacrylic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
PY138 ... C.I. pigment yellow 13 8 (quinophthalone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
BEPD:2-butyl-2-ethyl-1, ammediol
1,2-HD:1,2-hexylene glycol
TMP: TriMethylolPropane(TMP)
The result who puts down in writing from Table X II-1～Table X II-4 as can be known, under the situation of the ink for inkjet recording that has used embodiment XII-1～7, whole tests all is good result, yet if the ink for inkjet recording of reference example XII-1～7, in certain or a plurality of project of evaluation test, can't obtain good result.
[embodiment XIII]
(manufacturing of dispersion 1)
Dispersion 1 has been used as the Monarch 880 of Pigment black 7 (carbon black) (Cabot system).The powder of Monarch 880 is got wet,, used with the water wet condition with three roller runner milling mixings 3 hours.As pigment concentration is that 25% moistening pigment uses.
To possess agitator, thermometer, the reaction vessel of return line and dropping funnel with nitrogen replacement after, add vinylformic acid to 65 parts of cumyl phenoxy group glycol esters, 10 parts of benzyl acrylates, 2 parts in vinylformic acid, 0.3 part of t-lauryl mercaptan and be heated to 70 ℃, in dropping funnel, add the vinylformic acid of preparation in addition to 150 parts of cumyl phenoxy group glycol esters, 15 parts in vinylformic acid, 5 parts of butyl acrylates, 1 part of t-lauryl mercaptan, 1 part of the two isovaleronitrile of 20 parts of methyl ethyl ketones and azo make the dispersed polymeres polymerization reaction take place when dripping in reaction vessel with 4 hours.Then, in reaction vessel, add methyl ethyl ketone, made the dispersing polymer solution of 40% concentration.
In addition, with 40 parts of described dispersing polymer solutions with as the pigment concentration of the Monarch880 (Cabot system) of Pigment black 7 (carbon black) is 120 parts of moistening pigment, 100 parts of the aqueous sodium hydroxide solutions of 0.1mol/L, 30 parts of mixing of methyl ethyl ketone of 25%, uses ultra-high voltage homogenizer (the Sugino Machine of Co., Ltd. system Ultimizer HJP-25005) to carry out 8 with 200MPa about 1600g and takes turns dispersion.Afterwards, transfer in other container, add 300 parts of ion exchanged waters, stirred again 1 hour.After this, use rotatory evaporator that the part of the whole and water of methyl ethyl ketone is removed, be adjusted into pH8.5 with the sodium hydroxide neutralization of 0.1mol/L.Afterwards, filter, formed pigment concentration with the ion exchanged water adjustment and be 20% dispersion 1 with the film filter of 0.3 μ m.
(manufacturing of dispersion 2)
Dispersion 2 has been used pigment Blue 15: 1.Use the crude product of institute's synthetic pigment, by carrying out salt assistant research fellow mill with the pigment miniaturization.Thereafter, the desalting treatment of utilizing ion exchanged water clean to implement, dehydration concentrates and makes pigment concentration is 25% wet cake.Use and to have made dispersion 2 for wet cake.
To possess agitator, thermometer, the reaction vessel of return line and dropping funnel with nitrogen replacement after, add vinylformic acid to 65 parts of cumyl phenoxy group glycol esters, 10 parts of benzyl acrylates, 2 parts in vinylformic acid, 0.3 part of t-lauryl mercaptan and be heated to 70 ℃, in dropping funnel, add the vinylformic acid of preparation in addition to 150 parts of cumyl phenoxy group glycol esters, 15 parts in vinylformic acid, 5 parts of butyl acrylates, 1 part of t-lauryl mercaptan, 1 part of the two isovaleronitrile of 20 parts of methyl ethyl ketones and azo make the dispersed polymeres polymerization reaction take place when dripping in reaction vessel with 4 hours.Then, in reaction vessel, add methyl ethyl ketone, made the dispersing polymer solution of 40% concentration.
In addition, with 40 parts of described dispersing polymer solutions with as pigment Blue 15: 100 parts of the aqueous sodium hydroxide solutions of 120 parts of the wet cakes of 1 25% concentration, 0.1mol/L, 30 parts of mixing of methyl ethyl ketone, use ultra-high voltage homogenizer (the Sugino Machine of Co., Ltd. makes UltimizerHJP-25005) to carry out 8 about 1600g and take turns dispersion with 200MPa.Afterwards, transfer in other container, add 300 parts of ion exchanged waters, stirred again 1 hour.After this, use rotatory evaporator that the part of the whole and water of methyl ethyl ketone is removed, be adjusted into pH8.5 with the sodium hydroxide neutralization of 0.1mol/L.Afterwards, filter, formed pigment concentration with the ion exchanged water adjustment and be 20% dispersion 2 with the film filter of 0.3 μ m.
(manufacturing of dispersion 3)
Dispersion 3 is to use pigment violet 19 and dispersion 2 to make in the same manner.
(manufacturing of dispersion 4)
Dispersion 4 is not used the crude product of institute's synthetic pigment except using Pigment Yellow 73 74, beyond the operation by carrying out salt assistant research fellow mill with the pigment miniaturization, makes in the same manner with dispersion 2.
(embodiment XIII-1)
Made ink 1 by using dispersion 1 to mix with the vehicles composition shown in the Table X III-2.
(embodiment XIII-2)
Made ink 2 by using dispersion 2 to mix with the vehicles composition shown in the Table X III-2.
(embodiment XIII-3)
Made ink 3 by using dispersion 3 to mix with the vehicles composition shown in the Table X III-2.
(embodiment XIII-4)
Made ink 4 by using dispersion 4 to mix with the vehicles composition shown in the Table X III-2.
(reference example XIII-1)
Identical with dispersion 1, use is as the U.S. Cabot corporate system Monarch880 of carbon black (PBk7), vinylformic acid amount when making polymkeric substance used in the dispersion except reducing, use is made as acid number beyond 40 the polymkeric substance, make pigment dispersion 5 in the same manner with embodiment 1, made ink 5 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 1.
(reference example XIII-2)
Identical with dispersion 1, use is as the U.S. Cabot corporate system Monarch880 of carbon black (PBk7), vinylformic acid amount when making polymkeric substance used in the dispersion except increasing, use is made as acid number beyond 200 the polymkeric substance, make pigment dispersion 6 in the same manner with embodiment 1, made ink 6 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 1.
(reference example XIII-3)
Identical with reference example 1, use pigment Blue 15: 1 (trichlorine copper phthalocyanine: the system G500 of adret pigment Co., Ltd.), vinylformic acid amount when making polymkeric substance used in the dispersion except reducing, use is made as acid number beyond 40 the polymkeric substance, make pigment dispersion 7 in the same manner with embodiment 2, made ink 7 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-4)
Identical with reference example 2, use pigment Blue 15: 1 (trichlorine copper phthalocyanine: the system G500 of adret pigment Co., Ltd.), vinylformic acid amount when making polymkeric substance used in the dispersion except increasing, use is made as acid number beyond 200 the polymkeric substance, make pigment dispersion 8 in the same manner with embodiment 2, made ink 8 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-5)
Identical with reference example 1, use pigment violet 19 (quinoline a word used for translation ketone pigment: the Clariant system), vinylformic acid amount when making polymkeric substance used in the dispersion except reducing, use is made as acid number beyond 40 the polymkeric substance, make pigment dispersion 9 in the same manner with embodiment 3, made ink 9 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-6)
Identical with reference example 2, use pigment violet 19 (quinoline a word used for translation ketone pigment: the Clariant system), vinylformic acid amount when making polymkeric substance used in the dispersion except increasing, use is made as acid number beyond 200 the polymkeric substance, make pigment dispersion 10 in the same manner with embodiment 3, made ink 10 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-7)
Identical with reference example 1, use Pigment Yellow 73 74 (condensed azo-pigment: the Clariant system), vinylformic acid amount when making polymkeric substance used in the dispersion except reducing, use is made as acid number beyond 40 the polymkeric substance, make pigment dispersion 11 in the same manner with embodiment 4, made ink 11 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-8)
Identical with reference example 2, use Pigment Yellow 73 74 (condensed azo-pigment: the Clariant system), vinylformic acid amount when making polymkeric substance used in the dispersion except increasing, use is made as acid number beyond 200 the polymkeric substance, make pigment dispersion 12 in the same manner with embodiment 4, made ink 12 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-9)
Identical with dispersion 1, use is as the U.S. Cabot corporate system Monarch880 of carbon black (PBk7), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except increasing, use is made as the weight-average molecular weight of polymkeric substance beyond 15000 the polymkeric substance, make pigment dispersion 13 in the same manner with embodiment 1, made ink 13 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 1.
(reference example XIII-10)
Identical with dispersion 1, use is as the U.S. Cabot corporate system Monarch880 of carbon black (PBk7), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except reducing, use is made as the weight-average molecular weight of polymkeric substance beyond 110000 the polymkeric substance, make pigment dispersion 14 in the same manner with embodiment 1, made ink 14 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 1.
(reference example XIII-11)
Identical with reference example 1, use pigment Blue 15: 1 (trichlorine copper phthalocyanine: the system G500 of adret pigment Co., Ltd.), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except increasing, use is made as the weight-average molecular weight of polymkeric substance beyond 15000 the polymkeric substance, make pigment dispersion 15 in the same manner with embodiment 2, made ink 15 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-12)
Identical with reference example 2, use pigment Blue 15: 1 (trichlorine copper phthalocyanine: the system G500 of adret pigment Co., Ltd.), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except reducing, use is made as the weight-average molecular weight of polymkeric substance beyond 110000 the polymkeric substance, make pigment dispersion 16 in the same manner with embodiment 2, made ink 16 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-13)
Identical with reference example 1, use pigment violet 19 (quinoline a word used for translation ketone pigment: the Clariant system), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except increasing, use is made as the weight-average molecular weight of polymkeric substance beyond 15000 the polymkeric substance, make pigment dispersion 17 in the same manner with embodiment 3, made ink 17 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-14)
Identical with reference example 2, use pigment violet 19 (quinoline a word used for translation ketone pigment: the Clariant system), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except reducing, use is made as the weight-average molecular weight of polymkeric substance beyond 110000 the polymkeric substance, make pigment dispersion 18 in the same manner with embodiment 3, made ink 18 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-15)
Identical with reference example 1, use Pigment Yellow 73 74 (condensed azo-pigment: the Clariant system), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except increasing, use is made as the weight-average molecular weight of polymkeric substance beyond 15000 the polymkeric substance, make pigment dispersion 19 in the same manner with embodiment 4, made ink 19 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-16)
Identical with reference example 2, use Pigment Yellow 73 74 (condensed azo-pigment: the Clariant system), the amount of the two isovaleronitriles of azo when making polymkeric substance used in the dispersion except reducing, use is made as the weight-average molecular weight of polymkeric substance beyond 110000 the polymkeric substance, make pigment dispersion 20 in the same manner with embodiment 4, made ink 20 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 2.
(reference example XIII-17)
Identical with dispersion 1, use is as the U.S. Cabot corporate system Monarch880 of carbon black (PBk7), changed dispersive pressure except using the polymkeric substance identical and taken turns the number with dispersion 1, make pigment dispersion 21～26 in the same manner with embodiment 1, made ink 21～26 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 1.
(reference example XIII-18)
Identical with dispersion 2, use pigment Blue 15: 1 (trichlorine copper phthalocyanine: the system G500 of adret pigment Co., Ltd.), changed dispersive pressure except using the polymkeric substance identical and taken turns the number with dispersion 2, make pigment dispersion 27～32 in the same manner with embodiment 2, made ink 27～32 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 1.
(reference example XIII-19)
Identical with dispersion 3, use pigment violet 19 (quinoline a word used for translation ketone pigment: the Clariant system), changed dispersive pressure except using the polymkeric substance identical and taken turns the number with dispersion 3, make pigment dispersion 33～38 in the same manner with embodiment 1, made ink 33～38 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 3.
(reference example XIII-20)
Identical with dispersion 4, use Pigment Yellow 73 74 (condensed azo-pigment: the Clariant system), changed dispersive pressure except using the polymkeric substance identical and taken turns the number with dispersion 4, make pigment dispersion 39～44 in the same manner with embodiment 4, made ink 39～44 by mixing with the vehicles composition shown in the Table X III-2 in the same manner with embodiment 4.
(reference example XIII-21)
Except the U.S. Cabot corporate system Monarch880 that has used carbon black (PBk7) as powder, identical with embodiment 1, made ink 45 by mixing with the vehicles composition shown in the Table X III-2.
(reference example XIII-22)
Except having used the pigment Blue 15 of powder: 1 (the trichlorine copper phthalocyanine: identical the system G500 of adret pigment Co., Ltd.) with embodiment 2, made ink 46 by mixing with the vehicles composition shown in the Table X III-2.
(reference example XIII-23)
Except the pigment violet 19 that used powder (quinoline a word used for translation ketone pigment: identical the Clariant system) with embodiment 3, made ink 47 by mixing with the vehicles composition shown in the Table X III-2.
(reference example XIII-24)
Except the Pigment Yellow 73 74 that used powder (condensed azo-pigment: identical the Clariant system) with embodiment 4, made ink 48 by mixing with the vehicles composition shown in the Table X III-2.
(the ink-jet modulation example of paint ink)
Below, will be suitable for ink-jet and be shown among the Table X III-2 with the example of the composition of paint ink.Form ink-jet of the present invention and be to use the dispersion 1 of making, make by mixing with the vehicles composition shown in the Table X III-2 with described method with the adjustment of paint ink.And, used in the water of the residual amount in Table X III-1 and in ion exchanged water, added the 0.05% corrosive Topside 240 (Permachem Asia corporate system) that is used for preventing ink, 0.02% the corrosive benzotriazole that is used to prevent the ink gun member, 0.04% the water of EDTA (ethylenediamine tetraacetic acid (EDTA)) 2Na salt of influence of metal ion that is used to reduce ink system respectively.
(reference example XIII-25)
Except having changed the vehicles composition, identical with embodiment 1, made ink 49～54 by mixing with the vehicles composition shown in the Table X III-3.
(reference example XIII-26)
Except having changed the vehicles composition, identical with embodiment 2, made ink 55～60 by mixing with the vehicles composition shown in the Table X III-3.
(reference example XIII-27)
Except having changed the vehicles composition, identical with embodiment 3, made ink 61～66 by mixing with the vehicles composition shown in the Table X III-3.
(reference example XIII-28)
Except having changed the vehicles composition, identical with embodiment 4, made ink 67～72 by mixing with the vehicles composition shown in the Table X III-3.
(evaluation of dispersion stabilization)
Viscosity velocity of variation (%) and rate of descent (%) when the ink-jet of the different dispersion making of 60 ℃ of particle diameters that will use down pigment has been placed 30 days with paint ink are shown among the Table X III-1.Viscosity velocity of variation (%) expression when the dispersion stabilization conduct has been placed 30 days with each water-base ink under 60 ℃.Viscosity changes utilizes German Anton Paar system AMVn to measure down for 60 ° in angle, as percentage (%) expression of 1-(values after 30 days)/(value at initial stage).
(evaluation of common paper OD and glossy paper glossiness)
Used U.S. Xerox corporate system Xerox4024 paper as common paper, used Seiko Epson Corp's system photo paper＜gloss〉as glossy paper.Printer has used the ink-jet printer EM930C of Seiko Epson Corp's system, for common paper, use is estimated with the sample of the printing mode printing of the photographic printing quality of 720dpi, for glossy paper, use is estimated with the sample of the printing mode printing of the photographic printing quality of 1440dpi.The mensuration of OD is to use U.S. GRETAG corporate system GRETAG MACBETH SPECTROSCAN SPM-50 to carry out.The mensuration of glossiness is to make the system gloss tester IG-320 of Co., Ltd. of institute with the hole field mirror surface luster of the record surface of input angle 60 degree is measured, and each recording paper is got 5 times mean value.For medium, be Seiko Epson Corp's system photo paper＜gloss 〉, for printer, use the photographic printing quality printing of the system EM930C of Seiko Epson Corp with 720dpi.The results are shown among the Table X III-1.
(mensuration of ejection stability)
Use the system PX-V600 of Seiko Epson Corp as ink-jet printer, under 35 ℃ of 35% atmosphere, on the Xerox of Fuji corporate system XeroxP paper A4 version, utilize the Word of Microsoft with 100 pages of the ratio printings of the standard of character size 11, MSP Gothic, 4000 word/pages or leaves, estimate.The disorderly AA that is evaluated as will do not printed fully, to have a position the printing disorder be evaluated as A, to have 2～3 positions the printing disorder be evaluated as B, to have 4～5 positions the printing disorder be evaluated as C, the D that is evaluated as of the above printing disorder in 6 positions will be arranged, the results are shown among the Table X III-1.
Table X III-1
The result of the dispersion stabilization of embodiment 1, common paper OD, glossy paper glossiness and ejection stability
Figure BSA00000390083601761
Continuous
Figure BSA00000390083601771
Pressure: dispersive pressure (MPa), wheel: wheel number, Mw: weight-average molecular weight
Stability: storage stability, OD:OD value, gloss: glossy paper glossiness, ejection: ejection stability
Table X III-2
Each ink is formed (weight %)
Pigment P?B?k?7 P?B?15:1 P?V?19 P?Y?74
Embodiment 1, reference example 1,2,9,10,17 46.7 - - -
Embodiment 2, reference example 3,4,11,12,18 - 33.3 - -
Embodiment 3, reference example 5,6,13,14,19 - - 40 -
Embodiment 4. reference examples 7,8,15,16,20 - - - 40
TEGmBE 3 1 1 1
1，2-HD 3 4 4 4
Gl 10 15 10 10
TMP 4 7 5 5
S104 0.15 0.15 0.15 0.15
Ion exchanged water Residual amount Residual amount Residual amount Residual amount
PBk7:C.I. Pigment black 7
PB15:1:C.I. pigment Blue 15: 1
PV19:C.I. pigment violet 19
PY74: Pigment Yellow 73 74
TEGmBE: triglycol single-butyl ether
1,2-HD:1,2-hexylene glycol
Gl: glycerine
TMP: TriMethylolPropane(TMP)
S104:Surfinol 104 (day letter chemistry system acetylenic glycol class tensio-active agent)
Table X III-3
Each ink that has changed the vehicles composition is formed (weight %)
Figure BSA00000390083601791
[embodiment XIV]
(embodiment XIV-1)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 363.0 weight parts, propenoic methyl carbamate (Ebecrvl CL1039:DAICEL-CYTEC Co., Ltd. system) 120 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carry out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes, add Cyanine BlueG-500pure-A (C.I.PB15:1 then with the high speed dispersion device; Adret pigment Co., Ltd. system) 480.0 weight parts stirred 1 hour with the high speed dispersion device, had obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 5.0 μ m to carry out pressure filtration.Made ink for inkjet recording that ink Table X IV-2 shown in form example 1 thereafter.
(embodiment XIV-2)
Except substitutional crylic acid 50.4 weight parts, become 13.2 parts of methacrylic acids, vinylformic acid 36.5 weight parts, 120 parts of propenoic methyl carbamates (Ebecrvl CL1039:DAICEL-CYTEC Co., Ltd. system) are become beyond 120 parts of the epoxy acrylates (NK Oligoma EA-6320: Xin Zhong village chemistry system), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 2 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 32000.
(embodiment XIV-3)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 42.6 weight parts, 120 parts of propenoic methyl carbamates (Ebecrvl CL1039:DAICEL-CYTEC Co., Ltd. system) are become beyond 120 parts of the epoxy acrylates (NK Oligoma EA-6320: Xin Zhong village chemistry system), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 3 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 55mgKOH/g, and weight-average molecular weight is 48000.
(embodiment XIV-4)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 77.5 weight parts, 120 parts of propenoic methyl carbamates (Ebecrvl CL1039:DAICEL-CYTEC Co., Ltd. system) are become beyond 120 parts of the epoxy acrylates (NK Oligoma EA-6320: Xin Zhong village chemistry system), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 4 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 100mgKOH/g, and weight-average molecular weight is 29000.
(embodiment XIV-5)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 93.0 weight parts, 120 parts of propenoic methyl carbamates (Ebecrvl CL1039:DAICEL-CYTEC Co., Ltd. system) are become beyond 120 parts of the epoxy acrylates (NK Oligoma EA-6320: Xin Zhong village chemistry system), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 5 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 120mgKOH/g, and weight-average molecular weight is 34000.
(embodiment XIV-6)
Except replacing pigment concentration is Cyanine Blue G-500pure-A 480.0 weight parts of 25 weight %, become Monarch 880 (C.I.PBk7:Cabot system) in addition, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 13 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
(embodiment XIV-7)
Except replacing pigment concentration is Cyanine Blue G-500pure-A 480.0 weight parts of 25 weight %, become Monarch 880 (C.I.PBk7:Cabot system) in addition, carry out in the same manner with embodiment 2, made the ink for inkjet recording of the composition example 14 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 32000.
(embodiment XIV-8)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used beyond Pigment Violet GC227-A 120.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 19 shown in the Table X IV-2 with embodiment 1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
(embodiment XIV-9)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used beyond Pigment Violet GC227-A 120.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 20 shown in the Table X IV-2 with embodiment 2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 32000.
(embodiment XIV-10)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used FastYellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 120.0 weight parts, carries out in the same manner, make the ink for inkjet recording of the composition example 25 shown in the Table X IV-2 with embodiment 1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
(embodiment XIV-11)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used FastYellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 120.0 weight parts, carries out in the same manner, made the ink for inkjet recording of the composition example 26 shown in the Table X IV-2 with embodiment 2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 32000.
(reference example XIV-1)
Except substitutional crylic acid benzyl ester 363.0 weight parts and propenoic methyl carbamate 120 weight parts, become beyond benzyl acrylate 483.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 6 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 29000.
(reference example XIV-2)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 116.3 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 7 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 150mgKOH/g, and weight-average molecular weight is 34000.
(reference example XIV-3)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 155.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 8 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the polymkeric substance acid number of the ink for inkjet recording of gained is 200mgKOH/g, and weight-average molecular weight is 29000.
(reference example XIV-4)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 20.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 9 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 10000.
(reference example XIV-5)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 15.0 weight parts, carry out in the same manner with embodiment 2, made the ink for inkjet recording of the composition example 10 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 18000.
(reference example XIV-6)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 3.1 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 11 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 130000.
(reference example XIV-7)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 23.3 weight parts, 120 parts of propenoic methyl carbamates (Ebecrvl CL1039:DAICEL-CYTEC Co., Ltd. system) are become beyond 120 parts of the epoxy acrylates (NK Oligoma EA-6320: Xin Zhong village chemistry system), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 12 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 33000.
(reference example XIV-8)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 1, made the ink for inkjet recording of the composition example 15 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 34000.
(reference example XIV-9)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 5, made the ink for inkjet recording of the composition example 16 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 32000.
(reference example XIV-10)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 6, made the ink for inkjet recording of the composition example 17 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 130000.
(reference example XIV-11)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 7, made the ink for inkjet recording of the composition example 18 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 33000.
(reference example XIV-12)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 1, made the ink for inkjet recording of the composition example 21 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 130mgKOH/g, and weight-average molecular weight is 29000.
(reference example XIV-13)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 5, made the ink for inkjet recording of the composition example 22 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 18000.
(reference example XIV-14)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 6, made the ink for inkjet recording of the composition example 23 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 130000.
(reference example XIV-15)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 7, made the ink for inkjet recording of the composition example 24 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 33000.
(reference example XIV-16)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the FastYellow 7413-A480.0 weight part, carry out in the same manner with reference example 1, made the ink for inkjet recording of the composition example 27 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 130mgKOH/g, and weight-average molecular weight is 29000.
(reference example XIV-17)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the FastYellow 7413-A480.0 weight part, carry out in the same manner with reference example 5, made the ink for inkjet recording of the composition example 28 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 18000.
(reference example XIV-18)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the FastYellow 7413-A480.0 weight part, carry out in the same manner with reference example 6, made the ink for inkjet recording of the composition example 29 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 130000.
(reference example XIV-19)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the FastYellow 7413-A480.0 weight part, carry out in the same manner with reference example 7, made the ink for inkjet recording of the composition example 30 shown in the Table X IV-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 33000.
(evaluation test 1: the evaluation method of erasibility)
The ink for inkjet recording of embodiment XIV-1～11 and reference example XIV-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.Afterwards, carried out the rub stationarity evaluation test of this test body of scriber (line marker) with the fruit juice that has loaded 300g.The stationarity evaluation test is to carry out with following method,, uses described test body (photo with paper＜gloss 〉) that is, observes printing surface and its back side to be overlapped with the load of 300g and the extent of exfoliation of ink when moving with the speed of 1m/s.Even S moves the test body of also not peeling off fully for 3 times among the Table X IV-2, even AA moves also not peel off fully for 2 times, but when moving 3 times, then produce the slight test body of peeling off, A does not peel off when moving 1 time fully, when still moving 2 times, then produce the slight test body of peeling off, B has the slight test body of peeling off, and C has the test body of peeling off and shifting to the back side, and D has the test body of obviously peeling off and shifting to the back side.
(evaluation test 2: the evaluation method of common paper color emissivity)
The ink for inkjet recording of embodiment XIV-1～11 and reference example XIV-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, obtain testing body.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag company (U.S.) system), measure OD value of all kinds.The result as the value representation of OD value in Table X IV-1.
(evaluation test 3: the evaluation method of glossiness)
The ink for inkjet recording of embodiment XIV-1～11 and reference example XIV-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).Its result is shown among the Table X IV-1.
(evaluation test 4: the evaluation method of particle diameter)
Utilize laser particle size analysis device (Zetasizer 3000, Malvern company (Britain) system) to measure the median size of the particle in the ink for inkjet recording of embodiment XIV-1～11 and reference example XIV-1～19.
(evaluation test 5: the evaluation method of storage stability)
Utilize rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) to measure to have left standstill under the initial stage viscosity of pigment dispersion of ink for inkjet recording used in embodiment XIV-1～11 and reference example XIV-1～19 and 70 ℃ the viscosity after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table X IV-1.And, among the Table X IV-1, give monomer composition, polymerization starter and pigment and ink for ink-jet print used in the manufacturing ink for ink-jet print and form.
Table X IV-1
Figure BSA00000390083601891
Figure BSA00000390083601901
And the breviary symbol of representing among Table X IV-1～Table X IV-2 is as follows.
BZA: benzyl acrylate
AA: vinylformic acid
MAA: methacrylic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
URA: propenoic methyl carbamate (Ebecrvl CL1039:DAICEL-CYTEC Co., Ltd. system)
EPA: epoxy acrylate (NK Oligoma EA-6320: Xin Zhong village chemistry system)
PBk7:C.I. Pigment black 7 (carbon black)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PV19:C.I. pigment violet 19 (quinoline a word used for translation ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
BEPD:2-butyl-2-ethyl-1, ammediol
1,2-HD:1,2-hexylene glycol
TMP: TriMethylolPropane(TMP)
From the result of Table X IV-1 and Table X IV-2 as can be known, under the situation of the ink for inkjet recording that has used embodiment XIV-1～11, evaluation test 1～5 all is good result, yet under the situation of the ink for inkjet recording that has used reference example XIV-1～19, in certain or a plurality of project of evaluation test 1～5, or not good result.
[embodiment XV]
(embodiment XV-1)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 483.0 weight parts, vinylformic acid 38.8 weight parts and t-butylperoxy (2-ethylhexanoate) 7.5 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carry out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 50mgKOH/g, and weight-average molecular weight is 22000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes with the high speed dispersion device, adding pigment concentration then is the Cyanine Blue G-500pure-A (C.I.PB15:1 of 25 weight %; Adret pigment Co., Ltd. system) 480.0 weight parts stirred 1 hour with the high speed dispersion device, had obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (nanometer machine, Nanomizer corporate system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 180MPa.
Then, from the dispersible pigment dispersion that so obtains, utilize the underpressure distillation used vaporizer remove methyl ethyl ketone and water-part, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 2.5 μ m to carry out pressure filtration.
Make ink for inkjet that ink Table X V-2 shown in form routine A thereafter.
(embodiment XV-2)
Be made as 85.3 weight parts except substitutional crylic acid 38.8 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 8.2 weight parts, carry out in the same manner with embodiment 1, make the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 110mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(embodiment XV-3)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 77.5 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.88 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 50mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(embodiment XV-4)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 170.5 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.91 weight parts, carry out in the same manner with embodiment 1, make the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 110mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(embodiment XV-5)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example B shown in the Table X V-2.
(embodiment XV-6)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example B shown in the Table X V-2.
(embodiment XV-7)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 3, made the ink for inkjet of the composition example B shown in the Table X V-2.
(embodiment XV-8)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 4, made the ink for inkjet of the composition example B shown in the Table X V-2.
(embodiment XV-9)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example C shown in the Table X V-2.
(embodiment XV-10)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example C shown in the Table X V-2.
(embodiment XV-11)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 3, made the ink for inkjet of the composition example C shown in the Table X V-2.
(embodiment XV-12)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with embodiment 4, made the ink for inkjet of the composition example C shown in the Table X V-2.
(embodiment XV-13)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with embodiment 1.
(embodiment XV-14)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with embodiment 2.
(embodiment XV-15)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with embodiment 3.
(embodiment XV-16)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with embodiment 4.
(reference example XV-1)
Be made as 31.0 weight parts except substitutional crylic acid 38.8 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 7.1 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 40mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(reference example XV-2)
Be made as 100.8 weight parts except substitutional crylic acid 38.8 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 8.8 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 130mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(reference example XV-3)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 62.0 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.87 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 40mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(reference example XV-4)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 201.5 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.92 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 130mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(reference example XV-5)
Except the colo(u)rant dispersion slip is not to use high-pressure homogenizer, but by in ball mill (Ashizawa Finetec company), filling the ball of φ 0.05mm with 80% filling ratio, at rotating speed 5, beyond continuing to pass through 2 hours under the condition of 000rpm and disperseing, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 40mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(reference example XV-6)
Except the colo(u)rant dispersion slip is not to use high-pressure homogenizer, but by in ball mill (Ashizawa Finetec company), filling the ball of 0.05mm with φ 80% filling ratio, at rotating speed 5, beyond continuing to pass through 2 hours under the condition of 000rpm and disperseing, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 50mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(reference example XV-7)
Except the colo(u)rant dispersion slip is not to use high-pressure homogenizer, but by in ball mill (Ashizawa Finetec company), filling the ball of φ 0.05mm with 80% filling ratio, at rotating speed 5, beyond continuing to pass through 2 hours under the condition of 000rpm and disperseing, carry out in the same manner with embodiment 2, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 110mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(reference example XV-8)
Except the colo(u)rant dispersion slip is not to use high-pressure homogenizer, but by in ball mill (Ashizawa Finetec company), filling the ball of φ 0.05mm with 80% filling ratio, at rotating speed 5, beyond continuing to pass through 2 hours under the condition of 000rpm and disperseing, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 130mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 22000.
(reference example XV-9)
Except the colo(u)rant dispersion slip is not to use high-pressure homogenizer, but by in ball mill (Ashizawa Finetec company), filling the ball of φ 0.05mm with 80% filling ratio, at rotating speed 5, beyond continuing to pass through 2 hours under the condition of 000rpm and disperseing, carry out in the same manner with reference example 3, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 40mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(reference example XV-10)
Except the colo(u)rant dispersion slip is not to use high-pressure homogenizer, but by in ball mill (Ashizawa Finetec company), filling the ball of φ 0.05mm with 80% filling ratio, at rotating speed 5, beyond continuing to pass through 2 hours under the condition of 000rpm and disperseing, carry out in the same manner with embodiment 3, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 50mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(reference example XV-11)
Except the colo(u)rant dispersion slip is not to use high-pressure homogenizer, but by in ball mill (Ashizawa Finetec company), filling the ball of φ 0.05mm with 80% filling ratio, at rotating speed 5, beyond continuing to pass through 2 hours under the condition of 000rpm and disperseing, carry out in the same manner with embodiment 4, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 110mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(reference example XV-12)
Except the colo(u)rant dispersion slip is not to use high-pressure homogenizer, but by in ball mill (Ashizawa Finetec company), filling the ball of φ 0.05mm with 80% filling ratio, at rotating speed 5, beyond continuing to pass through 2 hours under the condition of 000rpm and disperseing, carry out in the same manner with reference example 4, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 130mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 115000.
(reference example XV-13)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts, and be made as beyond t-butylperoxy (2-ethylhexanoate) 7.9 weight parts, carry out in the same manner, made the ink for inkjet of the composition example A shown in the Table X V-2 with embodiment 1.In addition, get polymer composition solution-part, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 50mgKOH/g with the acid number of the solid substance of polymer composition, weight-average molecular weight is 18000.
(reference example XV-14)
Be made as 85.3 weight parts except substitutional crylic acid 38.8 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 8.6 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 110mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 18000.
(reference example XV-15)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 77.5 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.86 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 50mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 130000.
(reference example XV-16)
Be made as 966.0 weight parts except substitutional crylic acid benzyl ester 483.0 weight parts, substitutional crylic acid 38.8 weight parts and be made as 170.5 weight parts, substituted tert-butyl peroxy (2-ethylhexanoate) 7.5 weight parts in addition, and be made as beyond t-butylperoxy (2-ethylhexanoate) 2.89 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet of the composition example A shown in the Table X V-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the ink for ink-jet print of gained is 110mgKOH/g with the acid number of the solid substance of polymer composition, and weight-average molecular weight is 130000.
(reference example XV-17)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-18)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-19)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 3, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-20)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 4, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-21)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 5, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-22)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 6, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-23)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 7, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-24)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 8, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-25)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 9, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-26)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 10, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-27)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 11, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-28)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Monarch 800 (C.I.PBk7:Cabot system) 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 12, made the ink for inkjet of the composition example B shown in the Table X V-2.
(reference example XV-29)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 1, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-30)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 2, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-31)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 3, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-32)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond the Pigment Violet GC227-A480.0 weight part of 25 weight %, carry out in the same manner with reference example 4, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-33)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond the Pigment Violet GC227-A480.0 weight part of 25 weight %, carry out in the same manner with reference example 5, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-34)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 6, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-35)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 7, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-36)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond the Pigment Violet GC227-A480.0 weight part of 25 weight %, carry out in the same manner with reference example 8, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-37)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 9, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-38)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 10, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-39)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 11, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-40)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, and used pigment concentration is beyond Pigment Violet GC227-A 480.0 weight parts of 25 weight %, carry out in the same manner with reference example 12, made the ink for inkjet of the composition example C shown in the Table X V-2.
(reference example XV-41)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the FastYellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 1.
(reference example XV-42)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 2.
(reference example XV-43)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 3.
(reference example XV-44)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 4.
(reference example XV-45)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 5.
(reference example XV-46)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the FastYellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 6.
(reference example XV-47)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 7.
(reference example XV-48)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 8.
(reference example XV-49)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 9.
(reference example XV-50)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 10.
(reference example XV-51)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 11.
(reference example XV-52)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, be the Fast Yellow 7413-A (C.I.PY74 of 25 weight % and used pigment concentration; Adret pigment Co., Ltd. system) beyond 480.0 weight parts, carries out in the same manner, made the ink for inkjet of the composition example D shown in the Table X V-2 with reference example 12.
(evaluation test 1: the evaluation method of common paper color emissivity)
The ink for ink-jet print of embodiment XV-1～16 and reference example XV-1～52 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, obtain testing body.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag company (U.S.) system), measure OD value of all kinds.The result as the value representation of OD value in Table X V-1.
(evaluation test 2: the evaluation method of glossiness)
The ink for ink-jet print of embodiment XV-1～16 and reference example XV-1～52 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).Its result is shown among the Table X V-1.
(evaluation test 3: dispersed evaluation method)
Utilize laser particle size analysis device (Zetasizer 3000, Malvern company (Britain) system) to measure the median size of the particle in the ink for ink-jet print of embodiment XV-1～16 and reference example XV-1～52.Its result is shown among the Table X V-1.
(evaluation test 4: the evaluation method of storage stability)
Utilize rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) to measure ink for ink-jet print used in embodiment XV-1～16 and reference example XV-1～52 with the viscosity that has left standstill under the initial stage viscosity of pigment dispersion and 70 ℃ after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table X V-1.And, among the Table X V-1, give monomer composition, polymerization starter and pigment and ink for ink-jet print used in the manufacturing ink for ink-jet print and form.
Table X V-1
Figure BSA00000390083602061
Figure BSA00000390083602071
Table X V-2
Figure BSA00000390083602081
And the breviary symbol of representing among Table X V-1～Table X V-2 is as follows.
BZA: benzyl acrylate
AA: vinylformic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
PBk7:C.I. Pigment black 7 (carbon black)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PV19:C.I. pigment violet 19 (quinoline a word used for translation ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
BEPD:2-butyl-2-ethyl-1, ammediol
1,2-HD:1,2-hexylene glycol
TMP: TriMethylolPropane(TMP)
EDTA: disodium ethylene diamine tetraacetate
NM: nanometer machine (Nanomizer company)
BM: ball mill (Ashizawa Finetec company)
From the result of Table X V-1 and Table X V-2 as can be known, under the situation of the ink for ink-jet print that has used embodiment XV-1～16, evaluation test 1～5 all is good result, yet under the situation of the ink for ink-jet print that has used reference example XV-1～52, in certain or a plurality of project of evaluation test 1～5, or not good result.
[embodiment XVI]
(embodiment XVI-1)
After the separating flask inside of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel is with nitrogen replacement, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 363.0 weight parts, vinylbenzene 120 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carry out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 33000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes, add Cyanine BlueG-500pure-A (C.I.PB15:1 then with the high speed dispersion device; Adret pigment Co., Ltd. system) 480.0 weight parts stirred 1 hour with the high speed dispersion device, had obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 5.0 μ m to carry out pressure filtration.Made ink for inkjet recording that ink Table X VI-2 shown in form example 1 thereafter.
(embodiment XVI-2)
Except substitutional crylic acid 50.4 weight parts, become 13.2 parts of methacrylic acids, vinylformic acid 36.5 weight parts, 120 parts of vinylbenzene are become beyond 40 parts of 80 parts of vinylbenzene and the vinylbenzene macromonomer AS-6S (Toagosei Co., Ltd's system), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 2 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 31000.
(embodiment XVI-3)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 42.6 weight parts, 120 parts of vinylbenzene are become beyond 40 parts of 80 parts of vinylbenzene and the vinylbenzene macromonomer AS-6S (Toagosei Co., Ltd's system), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 3 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 55mgKOH/g, and weight-average molecular weight is 45000.
(embodiment XVI-4)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 77.5 weight parts, 120 parts of vinylbenzene are become beyond 40 parts of 80 parts of vinylbenzene and the vinylbenzene macromonomer AS-6S (Toagosei Co., Ltd's system), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 4 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 100mgKOH/g, and weight-average molecular weight is 27000.
(embodiment XVI-5)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 93.0 weight parts, 120 parts of vinylbenzene are become beyond 40 parts of 80 parts of vinylbenzene and the vinylbenzene macromonomer AS-6S (Toagosei Co., Ltd's system), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 5 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 120mgKOH/g, and weight-average molecular weight is 33000.
(embodiment XVI-6)
Except replacing pigment concentration is Cyanine Blue G-500pure-A 480.0 weight parts of 25 weight %, become Monarch 880 (C.I.PBk7:Cabot system) in addition, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 13 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 32000.
(embodiment XVI-7)
Except replacing pigment concentration is Cyanine Blue G-500pure-A 480.0 weight parts of 25 weight %, become Monarch 880 (C.I.PBk7:Cabot system) in addition, carry out in the same manner with embodiment 2, made the ink for inkjet recording of the composition example 14 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 30000.
(embodiment XVI-8)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used beyond Pigment Violet GC227-A 120.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 19 shown in the Table X VI-2 with embodiment 1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 32000.
(embodiment XVI-9)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used beyond Pigment Violet GC227-A 120.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 20 shown in the Table X VI-2 with embodiment 2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 31000.
(embodiment XVI-10)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used FastYellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 120.0 weight parts, carries out in the same manner, make the ink for inkjet recording of the composition example 25 shown in the Table X VI-2 with embodiment 1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 33000.
(embodiment XVI-11)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used FastYellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 120.0 weight parts, carries out in the same manner, made the ink for inkjet recording of the composition example 26 shown in the Table X VI-2 with embodiment 2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 31000.
(reference example XVI-1)
Except 120 parts of substitutional crylic acid benzyl ester 363.0 weight parts and vinylbenzene, become beyond benzyl acrylate 483.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 6 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 27000.
(reference example XVI-2)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 116.3 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 7 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 150mgKOH/g, and weight-average molecular weight is 32000.
(reference example XVI-3)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 155.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 8 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the polymkeric substance acid number of the ink for inkjet recording of gained is 200mgKOH/g, and weight-average molecular weight is 27000.
(reference example XVI-4)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 20.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 9 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 10000.
(reference example XVI-5)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 15.0 weight parts, carry out in the same manner with embodiment 2, made the ink for inkjet recording of the composition example 10 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 17000.
(reference example XVI-6)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 3.1 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 11 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 120000.
(reference example XVI-7)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 23.3 weight parts, 120 parts of vinylbenzene are become beyond 40 parts of 80 parts of vinylbenzene and the vinylbenzene macromonomer AS-6S (Toagosei Co., Ltd's system), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 12 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 32000.
(reference example XVI-8)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 1, made the ink for inkjet recording of the composition example 15 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 130mgKOH/g, and weight-average molecular weight is 27000.
(reference example XVI-9)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 5, made the ink for inkjet recording of the composition example 16 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 17000.
(reference example XVI-10)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 6, made the ink for inkjet recording of the composition example 17 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 120000.
(reference example XVI-11)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 7, made the ink for inkjet recording of the composition example 18 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 32000.
(reference example XVI-12)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 1, made the ink for inkjet recording of the composition example 21 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 130mgKOH/g, and weight-average molecular weight is 27000.
(reference example XVI-13)
Except replacing Cyanine Blue G-500pure-A480.0 weight part, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 5, made the ink for inkjet recording of the composition example 22 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 16000.
(reference example XVI-14)
Except replacing Cyanine Blue G-500pure-A480.0 weight part, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 6, made the ink for inkjet recording of the composition example 23 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 120000.
(reference example XVI-15)
Except replacing Cyanine Blue G-500pure-A480.0 weight part, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 7, made the ink for inkjet recording of the composition example 24 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 32000.
(reference example XVI-16)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the FastYellow 7413-A480.0 weight part, carry out in the same manner with reference example 1, made the ink for inkjet recording of the composition example 27 shown in the Table X VI-2.In addition, get polymer composition solution-part, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 130mgKOH/g, weight-average molecular weight is 27000.
(reference example XVI-17)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the FastYellow 7413-A480.0 weight part, carry out in the same manner with reference example 5, made the ink for inkjet recording of the composition example 28 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 17000.
(reference example XVI-18)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the FastYellow 7413-A480.0 weight part, carry out in the same manner with reference example 6, made the ink for inkjet recording of the composition example 29 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 120000.
(reference example XVI-19)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the FastYellow 7413-A480.0 weight part, carry out in the same manner with reference example 7, made the ink for inkjet recording of the composition example 30 shown in the Table X VI-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 31000.
(evaluation test 1: the evaluation method of erasibility)
The ink for inkjet recording of embodiment XVI-1～11 and reference example XVI-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.Afterwards, carried out the rub stationarity evaluation test of this test body of scriber with the fruit juice that has loaded 300g.The stationarity evaluation test is to carry out with following method,, uses described test body (photo with paper＜gloss 〉) that is, observes printing surface and its back side to be overlapped with the load of 300g and the extent of exfoliation of ink when moving with the speed of 1m/s.Even S moves the test body of also not peeling off fully for 3 times among the Table X VI-2, even AA moves also not peel off fully for 2 times, but when moving 3 times, then produce the slight test body of peeling off, A does not peel off when moving 1 time fully, when still moving 2 times, then produce the slight test body of peeling off, B has the slight test body of peeling off, and C has the test body of peeling off and shifting to the back side, and D has the test body of obviously peeling off and shifting to the back side.
(evaluation test 2: the evaluation method of common paper color emissivity)
The ink for inkjet recording of embodiment XVI-1～11 and reference example XVI-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, obtain testing body.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag company (U.S.) system), measure OD value of all kinds.The result as the value representation of OD value in Table X VI-1.
(evaluation test 3: the evaluation method of glossiness)
The ink for inkjet recording of embodiment XVI-1～11 and reference example XVI-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).Its result is shown among the Table X VI-1.
(evaluation test 4: the evaluation method of particle diameter)
Utilize laser particle size analysis device (Zetasizer 3000, Malvern company (Britain) system) to measure the median size of the particle in the ink for inkjet recording of embodiment XVI-1～11 and reference example XVI-1～19.
(evaluation test 5: the evaluation method of storage stability)
Utilize rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) to measure to have left standstill under the initial stage viscosity of pigment dispersion of ink for inkjet recording used in embodiment XVI-1～11 and reference example XVI-1～19 and 70 ℃ the viscosity after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table X VI-1.And, among the Table X VI-1, give monomer composition, polymerization starter and pigment and ink for ink-jet print used in the manufacturing ink for ink-jet print and form.
Table X VI-1
Figure BSA00000390083602181
Figure BSA00000390083602191
And the breviary symbol of representing among Table X VI-1～Table X VI-2 is as follows.
BZA: benzyl acrylate
AA: vinylformic acid
MAA: methacrylic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
ST: vinylbenzene
STM: vinylbenzene macromonomer AS-6S (Toagosei Co., Ltd's system)
PBk7:C.I. Pigment black 7 (carbon black)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PV19:C.I. pigment violet 19 (quinoline a word used for translation (two) ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triethylene glycol butyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
BEPD:2-butyl-2-ethyl-1, ammediol
1,2-HD:1,2-hexylene glycol
TMP: TriMethylolPropane(TMP)
From the result of Table X VI-1 and Table X VI-2 as can be known, under the situation of the ink for inkjet recording that has used embodiment XVI-1～11, evaluation test 1～5 all is good result, yet under the situation of the ink for inkjet recording that has used reference example XVI-1～19, in certain or a plurality of project of evaluation test 1～5, or not good result.
[embodiment XVII]
(embodiment XVII-1)
In the separating flask of the 2000ml that will possess whipping appts, return line, thermometer, dropping funnel with nitrogen replacement after, in separating flask, add diethylene glycol monomethyl ether 200.0 weight parts, when stirring, be warmed up to 80 ℃.Then, in dropping funnel, add diethylene glycol monomethyl ether 200.0 weight parts, benzyl acrylate 363.0 weight parts, lauryl acrylate 120 weight parts, vinylformic acid 50.4 weight parts and t-butylperoxy (2-ethylhexanoate) 4.8 weight parts, dripped in separating flask with 4 hours down and make it to react at 80 ℃.After finishing to drip, after having kept 1 hour, add t-butylperoxy (2-ethylhexanoate) 0.8 weight part, under 80 ℃, carry out reaction in 1 hour again with 80 ℃.Utilize underpressure distillation diethylene glycol monomethyl ether removed thereafter.After this, add methyl ethyl ketone 600.0 weight parts, obtained resin and formed admittedly and be divided into 50% polymer composition solution.Get the part of the polymer composition solution that so obtains, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the solid substance of the polymer composition of gained is 65mgKOH/g, and weight-average molecular weight is 33000.
Then, in polymer composition solution 120.0 weight parts of making like this, add 30% aqueous sodium hydroxide solution, 3.0 weight parts, stirred 5 minutes, add Cyanine BlueG-500pure-A (C.I.PB15:1 then with the high speed dispersion device; Adret pigment Co., Ltd. system) 480.0 weight parts stirred 1 hour with the high speed dispersion device, had obtained the colo(u)rant dispersion slip.After this, utilize ultra-high voltage homogenizer (miniature fluidizer, Mizuho Industrial Co., Ltd system) to repeat 10 this colo(u)rant dispersion slip and take turns dispersion, obtained dispersible pigment dispersion with the pressure of 200MPa.
Then, the part that methyl ethyl ketone and water are removed in the underpressure distillation of vaporizer has been used in utilization from the dispersible pigment dispersion that so obtains, utilize separating centrifuge (05P-21, Hitachi's system) with the 5000rpm centrifugation after 30 minutes, add ion exchanged water, pigment dispersion is adjusted into pigment concentration reaches 15 weight %.After this, use the film filter (Advantec corporate system) of 5.0 μ m to carry out pressure filtration.Made ink for inkjet recording that ink Table X VII-2 shown in form example 1 thereafter.
(embodiment XVII-2)
Except substitutional crylic acid 50.4 weight parts, become 13.2 parts of methacrylic acids, vinylformic acid 36.5 weight parts, 120 parts of lauryl acrylates are become beyond 120 parts of polyalkylene glycol acrylate 200 esters (vinylformic acid PEG200 ester), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 2 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 31000.
(embodiment XVII-3)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 42.6 weight parts, 120 parts of lauryl acrylates are become beyond 120 parts of polyalkylene glycol acrylate 200 esters (vinylformic acid PEG200 ester), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 3 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 55mgKOH/g, and weight-average molecular weight is 45000.
(embodiment XVII-4)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 77.5 weight parts, 120 parts of lauryl acrylates are become beyond 120 parts of polyalkylene glycol acrylate 200 esters (vinylformic acid PEG200 ester), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 4 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 100mgKOH/g, and weight-average molecular weight is 27000.
(embodiment XVII-5)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 93.0 weight parts, 120 parts of lauryl acrylates are become beyond 120 parts of polyalkylene glycol acrylate 200 esters (vinylformic acid PEG200 ester), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 5 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 120mgKOH/g, and weight-average molecular weight is 32000.
(embodiment XVII-6)
Except replacing pigment concentration is Cyanine Blue G-500pure-A 480.0 weight parts of 25 weight %, become Monarch 880 (C.I.PBk7:Cabot system) in addition, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 13 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 32000.
(embodiment XVII-7)
Except replacing pigment concentration is Cyanine Blue G-500pure-A 480.0 weight parts of 25 weight %, become Monarch 880 (C.I.PBk7:Cabot system) in addition, carry out in the same manner with embodiment 2, made the ink for inkjet recording of the composition example 14 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 30000.
(embodiment XVII-8)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used beyond Pigment Violet GC227-A 120.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 19 shown in the Table X VII-2 with embodiment 1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 32000.
(embodiment XVII-9)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used beyond Pigment Violet GC227-A 120.0 weight parts, carried out in the same manner, made the ink for inkjet recording of the composition example 20 shown in the Table X VII-2 with embodiment 2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 31000.
(embodiment XVII-10)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used FastYellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 120.0 weight parts, carries out in the same manner, make the ink for inkjet recording of the composition example 25 shown in the Table X VII-2 with embodiment 1.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 33000.
(embodiment XVII-11)
Except replacement Cyanine Blue G-500pure-A 120.0 weight parts, and used FastYellow 7413-A (C.I.PY74; Adret pigment Co., Ltd. system) beyond 120.0 weight parts, carries out in the same manner, made the ink for inkjet recording of the composition example 26 shown in the Table X VII-2 with embodiment 2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 31000.
(reference example XVII-1)
Except 120 parts of substitutional crylic acid benzyl ester 363.0 weight parts and lauryl acrylates, become beyond benzyl acrylate 483.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 6 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 27000.
(reference example XVII-2)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 116.3 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 7 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 150mgKOH/g, and weight-average molecular weight is 32000.
(reference example XVII-3)
Except substitutional crylic acid 50.4 weight parts, become beyond vinylformic acid 155.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 8 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the polymkeric substance acid number of the ink for inkjet recording of gained is 200mgKOH/g, and weight-average molecular weight is 27000.
(reference example XVII-4)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 20.0 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 9 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 10000.
(reference example XVII-5)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 15.0 weight parts, carry out in the same manner with embodiment 2, made the ink for inkjet recording of the composition example 10 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 17000.
(reference example XVII-6)
Except substituted tert-butyl peroxy (2-ethylhexanoate) 4.8 weight parts, become beyond t-butylperoxy (2-ethylhexanoate) 3.1 weight parts, carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 11 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 120000.
(reference example XVII-7)
Except substitutional crylic acid 50.4 weight parts, become vinylformic acid 23.3 weight parts, 120 parts of lauryl acrylates are become beyond 120 parts of the Macrogol 200 acrylate (PEG200 acrylate), carry out in the same manner with embodiment 1, made the ink for inkjet recording of the composition example 12 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 32000.
(reference example XVII-8)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 1, made the ink for inkjet recording of the composition example 15 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 130mgKOH/g, and weight-average molecular weight is 27000.
(reference example XVII-9)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 5, made the ink for inkjet recording of the composition example 16 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 17000.
(reference example XVII-10)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 6, made the ink for inkjet recording of the composition example 17 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 120000.
(reference example XVII-11)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, become beyond Monarch880 (C.I.PBk7:Cabot system) 480.0 weight parts, carry out in the same manner with reference example 7, made the ink for inkjet recording of the composition example 18 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 32000.
(reference example XVII-12)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 1, made the ink for inkjet recording of the composition example 21 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 130mgKOH/g, and weight-average molecular weight is 27000.
(reference example XVII-13)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 5, made the ink for inkjet recording of the composition example 22 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 16000.
(reference example XVII-14)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 6, made the ink for inkjet recording of the composition example 23 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 120000.
(reference example XVII-15)
Except replacing Cyanine Blue G-500pure-A480.0 weight part, used beyond PigmentViolet GC227-A 480.0 weight parts, carry out in the same manner with reference example 7, made the ink for inkjet recording of the composition example 24 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 32000.
(reference example XVII-16)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the FastYellow 7413-A480.0 weight part, carry out in the same manner with reference example 1, made the ink for inkjet recording of the composition example 27 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 130mgKOH/g, and weight-average molecular weight is 27000.
(reference example XVII-17)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond the FastYellow 7413-A480.0 weight part, carry out in the same manner with reference example 5, made the ink for inkjet recording of the composition example 28 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 60mgKOH/g, and weight-average molecular weight is 17000.
(reference example XVII-18)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond FastYellow 7413-A 480.0 weight parts, carry out in the same manner with reference example 6, made the ink for inkjet recording of the composition example 29 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 65mgKOH/g, and weight-average molecular weight is 120000.
(reference example XVII-19)
Except replacing Cyanine Blue G-500pure-A 480.0 weight parts, used beyond FastYellow 7413-A 480.0 weight parts, carry out in the same manner with reference example 7, made the ink for inkjet recording of the composition example 30 shown in the Table X VII-2.In addition, get the part of polymer composition solution, dry after 1 hour in 105 ℃ heat-flash drying machine, the acid number of the polymkeric substance of the ink for inkjet recording of gained is 30mgKOH/g, and weight-average molecular weight is 31000.
(evaluation test 1: the evaluation method of erasibility)
The ink for inkjet recording of embodiment XVII-1～11 and reference example XVII-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.Afterwards, carried out the rub stationarity evaluation test of this test body of scriber with the fruit juice that has loaded 300g.The stationarity evaluation test is to carry out with following method,, uses described test body (photo with paper＜gloss 〉) that is, observes printing surface and its back side to be overlapped with the load of 300g and the extent of exfoliation of ink when moving with the speed of 1m/s.Even AA moves the test body of also not peeling off fully for 2 times among the Table X VI-2, A does not peel off when moving 1 time fully, but when moving 2 times, then produce the slight test body of peeling off, B has the slight test body of peeling off, C has the test body of peeling off and shifting to the back side, and D has the test body of obviously peeling off and shifting to the back side.
(evaluation test 2: the evaluation method of common paper color emissivity)
The ink for inkjet recording of embodiment XVII-1～11 and reference example XVII-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), on XeroxP paper (Xerox of Fuji corporate system), print on the spot, obtain testing body.Printing model is with print paper: common paper, and print quality: hyperfine, color correct: do not have Print direction: two-way and carry out.After this, use GRETAGMACBETH SPECTROSCAN SP50 (Gretag company (U.S.) system), measure OD value of all kinds.The result as the value representation of OD value in Table X VII-1.
(evaluation test 3: the evaluation method of glossiness)
The ink for inkjet recording of embodiment XVII-1～11 and reference example XVII-1～19 is used ink-jet printer (EM-930C, Seiko Epson Corp's system), at photo with paper＜gloss print on the spot on (Seiko Epson Corp's system), obtained the test body.Printing model is with print paper: xerox and use paper, print quality: photo, color correct: nothing, Print direction: two-way and carry out.20 degree gloss of this test body have been measured with glossmeter (HG-268, Suga trier Co., Ltd. system).Its result is shown among the Table X VII-1.
(evaluation test 4: the evaluation method of particle diameter)
Utilize laser particle size analysis device (Zetasizer 3000, Malvern company (Britain) system) to measure the median size of the particle in the ink for inkjet recording of embodiment XVII-1～11 and reference example XVII-1～19.
(evaluation test 5: the evaluation method of storage stability)
Utilize rolling-ball viscometer (AMVn, Anton Paar (Germany) corporate system) to measure to have left standstill under the initial stage viscosity of pigment dispersion of ink for inkjet recording used in embodiment XVII-1～11 and reference example XVII-1～19 and 70 ℃ the viscosity after 1 week.With its result as storage stability: the value representation that has left standstill viscosity (the mPas)/initial stage viscosity (mPas) after 1 week under 70 ℃ is in Table X VII-1.And, among the Table X VII-1, give monomer composition, polymerization starter and pigment and ink for inkjet recording used in the manufacturing ink for ink-jet print and form.
Table X VII-1
Figure BSA00000390083602291
Figure BSA00000390083602301
And the breviary symbol of representing among Table X VII-1～Table X VII-2 is as follows.
BZA: benzyl acrylate
AA: vinylformic acid
MAA: methacrylic acid
BPEH: t-butylperoxy (2-ethylhexanoate)
LA: lauryl acrylate
PEG200A: Macrogol 200 acrylate
PBk7:C.I. Pigment black 7 (carbon black)
PB15:1:C.I. pigment Blue 15: 1 (trichlorine phthalocyanine)
PV19:C.I. pigment violet 19 (quinoline a word used for translation ketone)
PY74:C.I. Pigment Yellow 73 74 (condensed azo-pigment)
DEGmBE: diethylene glycol monobutyl ether
TEGmBE: triglycol monobutyl ether
PGmBE: propylene glycol monobutyl ether
DPGmBE: dipropylene glycol monobutyl ether
BEPD:2-butyl-2-ethyl-1, ammediol
1,2-HD:1,2-hexylene glycol
TMP: TriMethylolPropane(TMP)
From the result of Table X VII-1 and Table X VII-2 as can be known, under the situation of the ink for inkjet recording that has used embodiment XVII-1～11, evaluation test 1～5 all is good result, yet under the situation of the ink for inkjet recording that has used reference example XVII-1～19, in certain or a plurality of project of evaluation test 1～5, or not good result.
The present invention is to be willing to 2004-307763 the spy of Japan's application on October 22nd, 2004, on March 29th, 2005, the spy in Japan's application was willing to 2005-094813, on March 29th, 2005, the spy in Japan's application was willing to 2005-094818, on March 29th, 2005, the spy in Japan's application was willing to 2005-094819, on March 29th, 2005, the spy in Japan's application was willing to 2005-094820, on October 5th, 2005, the spy in Japan's application was willing to 2005-292131, on October 5th, 2005, the spy in Japan's application was willing to 2005-292132, on October 5th, 2005, the spy in Japan's application was willing to 2005-292133, on October 5th, 2005, the spy in Japan's application was willing to 2005-292134, on October 5th, 2005, the spy in Japan's application was willing to 2005-292135, on October 5th, 2005, the spy in Japan's application was willing to 2005-292136, on October 5th, 2005, the spy in Japan's application was willing to 2005-292139, on October 5th, 2005, the spy in Japan's application was willing to 2005-292140, on October 5th, 2005, the spy in Japan's application was willing to 2005-292141, on October 5th, 2005, the spy in Japan's application was willing to 2005-292142, on October 5th, 2005, the spy in Japan's application was willing to 2005-292144, on October 5th, 2005, the spy in Japan application was willing to 2005-292145 as the basis of advocating right of priority, by reference their full content was enrolled.
The industrial possibility of utilizing
The present invention can be for the making of the record thing that utilizes ink jet recording method to carry out.

Claims (30)

1. ink for inkjet recording, contain water and pigment, wherein pigment is to use following polymer dispersed, promptly, as the constituent of polymkeric substance is that benzyl acrylate more than the 50 weight % and/or cyclohexyl acrylate and (methyl) vinylformic acid below the 20 weight % are aggregated at least, and described pigment is PY74 as yellow ultramarine, is to be selected from more than at least a among PV19, PR122, PR177 and the PR254 as magenta pigment, or is PB 15:1 as green pigment.
2. ink for inkjet recording according to claim 1, wherein, the weight-average molecular weight of described polymkeric substance is more than 20000 below 200000.
3. ink for inkjet recording according to claim 1 and 2, wherein, contain the above 1 weight % of 0.05 weight % following be selected from 2,4,7,9-tetramethyl--5-decine-4,7-glycol, 3,6-dimethyl-4-octyne-3,6-glycol, 2,4,7,9-tetramethyl--5-decine-4, the alkylene oxide affixture and 3 of 7-glycol, 6-dimethyl-4-octyne-3, more than one in the alkylene oxide affixture of 6-glycol.
4. ink for inkjet recording according to claim 1, it is characterized in that, contain water and pigment, wherein pigment is to use following polymer dispersed, promptly, constituent as polymkeric substance is that the benzyl acrylate more than the 50 weight %, (methyl) vinylformic acid below the 15 weight % are aggregated at least, and this polymkeric substance has the following acid number of the above 120mgKOH/g of 50mgKOH/g, and its weight-average molecular weight is more than 20000 below 120000.
5. ink for inkjet recording according to claim 1, wherein, the dispersion particle diameter of described yellow ultramarine is below the above 110nm of 90nm, and the one-level particle diameter is below the above 80nm of 30nm.
6. ink for inkjet recording according to claim 1 or 5, wherein, the dispersion particle diameter of described magenta pigment is below the above 100nm of 20nm, and the one-level particle diameter is below the above 70nm of 20nm.
7. ink for inkjet recording according to claim 1 or 5, wherein, the dispersion particle diameter of described green pigment is below the above 100nm of 20nm, and the one-level particle diameter is below the above 70nm of 20nm.
8. ink for inkjet recording according to claim 4 is characterized in that, contains the following TriMethylolPropane(TMP) of the above 20 weight % of 1 weight %.
9. ink for inkjet recording according to claim 4 wherein, contains the following 2-butyl-2-ethyl-1 of the above 10 weight % of 0.1 weight %, ammediol.
10. ink for inkjet recording according to claim 4, wherein, also contain at least a of the resin particle that constitutes by following polymkeric substance with the form of resin emulsion, promptly, as the constituent of polymkeric substance is that benzyl acrylate more than the 50 weight % and (methyl) vinylformic acid below the 15 weight % are aggregated at least, and this polymkeric substance has the acid number of 50～120mgKOH/g, and its weight-average molecular weight is more than 20000 below 120000.
11. ink for inkjet recording according to claim 10, wherein, used polymkeric substance represents to use more than 50% and the identical polymkeric substance of the constituent polymkeric substance that uses as described pigment dispersing agent with the weight conversion ratio in the described resin emulsion.
12. according to claim 10 or 11 described ink for inkjet recording, wherein, the median size of the resin particle that contains as described resin emulsion is 30～150nm.
13. according to claim 10 or 11 described ink for inkjet recording, wherein, the resin particle that contains as described resin emulsion is contained with 0.1～10 weight % with respect to the ink total amount.
14. ink for inkjet recording according to claim 4 wherein, contains at least:
1) C of 0.5～15 weight % 4～C 101, the 2-alkylene glycol;
2) 5～30 weight % remove described 1, the C beyond the 2-alkylene glycol 10Following polyalcohols.
15. ink for inkjet recording according to claim 14 is wherein described 1, the content of 2-alkylene glycol and described polyalcohols and be 6～40 weight %.
16. according to claim 14 or 15 described ink for inkjet recording, wherein described 1, the ratio that contains of 2-alkylene glycol and described polyalcohols is 1: 50～1: 1.5 a scope.
17. according to claim 14 or 15 described ink for inkjet recording, wherein, contain 0.5～15 weight % with R 1O-(C mH 2mO) n-R 2The gylcol ether of expression, wherein m and n are the integer more than 1, m * n≤10, R 1And R 2Be C 8Following alkyl, R 1And R 2Both can be the same or different.
18. ink for inkjet recording according to claim 17, wherein described 1, the ratio that contains of 2-alkylene glycol and described gylcol ether is 10: 1 :～1: 10 scope.
19. ink for inkjet recording according to claim 17, wherein described 1, the content sum of 2-alkylene glycol, described polyalcohols and described gylcol ether is 7～40 weight %.
20. ink for inkjet recording according to claim 4 wherein, contains the pigment dispersion that forms at the described polymkeric substance of self-dispersion type pigment particles finishing.
21. ink for inkjet recording according to claim 4 wherein, as described pigment, uses C.I. pigment yellow 13 8 at least.
22. ink for inkjet recording according to claim 21 wherein, as described pigment, also uses C.I. Pigment Yellow 73 74.
23. ink for inkjet recording according to claim 22, wherein, the containing of C.I. pigment yellow 13 8 and C.I. Pigment Yellow 73 74 than being scaled 20: 1 with weight～1: 10 scope.
24. ink for inkjet recording according to claim 4 wherein, as the constituent of described polymkeric substance, also contains epoxy (methyl) acrylate and/or (methyl) propenoic methyl carbamate more than 10%.
25. ink for inkjet recording according to claim 4 wherein, as the constituent of described polymkeric substance, also contains styrene monomer and/or vinylbenzene macromonomer more than 10%.
26. ink for inkjet recording according to claim 4 wherein, as the constituent of described polymkeric substance, contains (methyl) alkyl acrylate and/or (methyl) vinylformic acid alkylene diol ester more than 10%.
27. according to any described ink for inkjet recording in the claim 4～5,8～11,14～15 and 20～26, wherein, contain the above 1 weight % of 0.05 weight % following be selected from 2,4,7,9-tetramethyl--5-decine-4,7-glycol and 2,4,7,9-tetramethyl--5-decine-4, more than one in the alkylene oxide affixture of 7-glycol.
28., wherein, contain 1, the 2-alkylene glycol according to any described ink for inkjet recording in the claim 1～2,4～5,8～11 and 20～26.
29., wherein, contain and be selected from two (three) ethylene glycol monobutyl ethers and (two) propylene glycol monobutyl ether more than one according to any described ink for inkjet recording in the claim 1～2,4～5,8～11,14～15 and 20～26.
30., wherein, contain 2-butyl-2-ethyl-1, ammediol according to any described ink for inkjet recording in the claim 1～2,4～5,8,10～11,14～15 and 20～26.
CN 201010592959 2004-10-22 2005-10-24 Inkjet recording ink Pending CN102002283A (en)

Applications Claiming Priority (27)

Application Number Priority Date Filing Date Title
JP2004-307763 2004-10-22
JP2004307763A JP4853606B2 (en) 2004-10-22 2004-10-22 Ink for inkjet recording
JP2005-094820 2005-03-29
JP2005094820A JP4687188B2 (en) 2005-03-29 2005-03-29 Ink for inkjet recording
JP2005-094818 2005-03-29
JP2005094818A JP4687187B2 (en) 2005-03-29 2005-03-29 Ink for inkjet recording
JP2005094813A JP4715270B2 (en) 2005-03-29 2005-03-29 Ink for inkjet recording
JP2005-094813 2005-03-29
JP2005094819A JP4715271B2 (en) 2005-03-29 2005-03-29 Ink for ink jet recording and ink set
JP2005-094819 2005-03-29
JP2005292142A JP2007099920A (en) 2005-10-05 2005-10-05 Manufacturing method of pigment dispersion and inkjet recording ink comprising pigment dispersion
JP2005292140A JP2007099918A (en) 2005-10-05 2005-10-05 Method for producing ink for inkjet recording
JP2005-292134 2005-10-05
JP2005-292135 2005-10-05
JP2005-292139 2005-10-05
JP2005-292144 2005-10-05
JP2005-292141 2005-10-05
JP2005292141A JP4862341B2 (en) 2005-10-05 2005-10-05 Ink for inkjet recording
JP2005-292136 2005-10-05
JP2005-292145 2005-10-05
JP2005292145A JP2007099923A (en) 2005-10-05 2005-10-05 Ink for inkjet recording
JP2005-292140 2005-10-05
JP2005-292133 2005-10-05
JP2005-292132 2005-10-05
JP2005-292131 2005-10-05
JP2005-292142 2005-10-05
JP2005292144A JP2007099922A (en) 2005-10-05 2005-10-05 Ink for inkjet recording

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104884549A (en) * 2012-12-18 2015-09-02 花王株式会社 Ink-jet printing method
CN106009921A (en) * 2015-03-30 2016-10-12 富士胶片株式会社 Pigment dispersion for ink jetting, method of producing the same, ink set, and image forming method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104884549A (en) * 2012-12-18 2015-09-02 花王株式会社 Ink-jet printing method
CN106009921A (en) * 2015-03-30 2016-10-12 富士胶片株式会社 Pigment dispersion for ink jetting, method of producing the same, ink set, and image forming method

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