Inkjet ink, inkjet recording method, ink cartridge, recording unit and inkjet recorder

0001The ink for specification Ing jets, an ink jet recording method, an ink cartridge, a recording unit, and an ink-jet recording device

0002Technical field

0003it has the present invention and high surrounding gas-proof nature -- and the time of printing on a recording medium -- gold the so-called generating of Genus gloss and a bronze phenomenon was controlled -- a good picture can be obtained It is related with the ink for To ink-jets. The present invention and the above-mentioned Í for ink-jets The ink jet recording method using An, an ink cartridge, and Recording unit and It is related with a Facial expression ink-jet recording device. Background art

0004an ink jet recording method and an ink glob -- a regular paper, gloss media, etc. it gives on a recording medium -- it is a record method which forms a picture -- the low-pricing and record By improvement in speed, spread is progressing quickly. high-definition-izing of the recorded image having progressed -- in addition, it follows on the rapid spread of digital cameras -- a film photo -- Comparable Popularity is widely gained as the output method of a Photo picture.

0005The formation of the minimum drop of recent years and an ink droplet, improvement in Color gamut accompanying introduction of multicolor ink, etc. High definition-ization is progressing more than Ri and former. on the other hand, Color material, Inc. -- an opposite -- the demand to carry out becomes larger -- reliance of color-enhancing improvement, a clog, discharge stability, etc. The severer characteristic is demanded in the sex.

0006On the other hand, the image keeping quality of the recorded matter obtained by the problem of the ink jet recording method at the time of comparing with a film photo is mentioned. Being general and ink jet recording method The obtained recorded matter compares with a film photo, the image keeping quality is low -- recorded matter It is record when light, humidity, heat, the surrounding gas that exists in the air, etc. Mischief for a long time. the color material on a thing deteriorates -- the problem of being easy to generate color tone change and fading of a picture -- When. Raising surrounding gas-proof nature to the level of a film photo especially, and ink It was a subject from the former in a jet recording method. Í for ink-jets the inside of . which is the hue used as An, a yellow, the Mazen evening, and cyanogen -- most -- It is cyanogen that surrounding gas-proof nature is inferior. This It was , surrounding gas-proof of Cyanogen, Inc. It is one of the important issues in the ink-jet recording method to raise a sex to a level equivalent to Hierro r Check Magenta, Inc.

0007The basic frame of the color material of the ink for ink-jets which has cyanogen hue, and Phantasy It is divided roughly into two, a Fanin frame and a truffe enyl methane skeleton. the former typical color there are C. I. D ir e c t B l u e 86, 87, and a C. I. D i r e c t B 1 u e 199 grade in material -- there is a C. I .Ac i d B l ue 9 grade in the latter typical color material again.

0008being general and a phthalocyanine system color material are compared with . triphenylmethane series color material -- there is the feature of excelling in lightfastness. a phthalocyanine system color material, humidity, and heat the receiving degree of solidity is high -- ink for ink-jets since color enhancement is good It is widely used as a color material.

0009However, a phthalocyanine system color material and the surrounding gas in the air (ozone, NO)_xS 0₂There is a tendency for the degree of solidity especially to ozone gas to be inferior. To the recorded matter printed to the recording medium which has an ink absorbing layer containing inorganic substances, such as alumina and silica, especially The lowness of robustness which can be set is Fading remarkably, when being remarkable and a recorded matter are neglected indoors for a long time. A color will be carried out. In order to raise this surrounding gas-proof nature and to add in ink Various compounds are indicated. (For example, Provisional Publication No. [ -- Refer to No. 249677 gazette. ] 5 -- 17 No. 1085 gazette, Provisional-Publication-No. 1 1 1 No. 29729 gazette, and Provisional Publication No. 10 -- No. 130517 gazette, provisional-publication-of-a-patent 20 00 No. -303009 gazette, and provisional publication of a patent 2002). however, as high as the good color enhancement as ink for ink Jeetsu ♪ in any case -- -proof -- The actual condition has not accomplished coexistence of surrounding gas nature.

0010furthermore -- also obtaining that of a The evening Russia Nin system color material -- one subject -- the height of the coherence of a color material -- Cause There is the so-called generating of the metallic luster which carries out Cause, and a bronze phenomenon. in a recorded matter -- Belon the optical reflective characteristic changes the case where a A phenomenon occurs -- the color enhancement of a picture, and hue -- work it spreads -- it changes -- remarkable deterioration of picture grace is caused. This bronze phenomenon and inn It is [ the height of the coherence of the color material in the inside of ink, and ] record intermediation when The is given to a recording medium. Due to the fall of the perviousness of the ink to the body, etc., a color material condenses in the recording-medium surface. It is thought that it generates in a sake. In particular, it is among the molecule at the object of improving surrounding gas-proof nature. In the ink containing the color material with which the Amino machine was introduced, and a color material with low solubility to water There is a tendency for generating of a bronze phenomenon to become remarkable. . Improve Green gas by using a specific phthalocyanine system color material. with the proposal to make (for example, refer to Patent 2 9 4 2 3 1 No. 9 gazette). This specific Off 1 of a subject [ in / by using an evening Russia Nin system color material / a phthalocyanine system color material ] The surrounding gas-proof nature which is One is obtained. however -- the above-mentioned proposal -- a bronze phenomenon -- about there is no Mention -- about the bronze-proof nature, it is unknown. That is, bronze-proof They are a sex and surrounding gas-proof nature, and the subject it is [ the subject ] yet incompatible.

0011therefore, it excels in color enhancement -- it has high surrounding gas-proof nature -- further -- Depart of a bronze phenomenon Search of the ink for ink Jeetsu ♪ using the phthalocyanine system color material with which the student was controlled Cord has been an indispensable subject. The indication of an invention

0012Then, compound by which these artificers are expressed with the above-mentioned general formula (I) with high surrounding gas-proof nature Or substitution combined with the phthalocyanine frame when the salt was examined It found out that Pronz may occur with the ratio of a machine, etc.

0013therefore, the metallic luster at the time of printing on the object of the present invention, and a recording medium and what is called The generating of the mouth S phenomenon was controlled -- ink Jesse which can obtain a good picture It is in providing the ink for A.

0014This which provides the record method using the another object and the above-mentioned ink for ink-jets, the recording unit, ink cartridge, and ink-jet recording device of the present invention It is.

0015It is achievement To be sick by the above-mentioned object and the following present invention. Namely, Í concerning the present invention Ink for An ink jet, Inn for ink-jets which contains a color material at least It is Ah with the compound by which the above-mentioned color material is expressed with following general formula (I) in The, or its salt. It is [ Ri and ] the feature further about containing the Amin compound denoted by the following general formula (I I). It carries out.

0016General formula (I)

0017<img file="WO2006011663A1_D0001.tif" />

0018(General formula (I) Inside and M being an alkaline metal or ammonium. R)₂They are a hydrogen atom, a sulfonic group, and a carboxyl group to Each one independence. (however, R being R)₂The same the case where it becomes a hydrogen atom is sometimes excluded -- it is -- Y -- chlorine atom, a hydroxyl machine, a Amino machine, and mono-or are dialkylamino groups -- 1, m, and n -- respectively -- 1 = 0*2, m=l*3, and n=l*3 (however, l+m+n = 3*4) it is -- substitution machine A substitution position is only the 4th place or 4'. General formula (I I)

0019N R 1 Ft

0020(Inside of a general formula (I I), R)₂R₃A hydrogen atom, a Alkyl machine, a hydroxy low-grade Alkyl machine, a cyclohexyl machine, and mono-or are a Dialkylamino alkyl machine, a Shano low-grade Alkyl machine, and a phenyl group that may be replaced at Are independence (however, R R).₂R₃The case where All serves as a hydrogen atom is excluded.

0021It is Í about the ink jet recording method concerning another embodiment of the present invention, and ink. In Cug which has the process of breathing out by the Nunjet method and recording on a recording medium In a Tut record method, above-mentioned Inc. is in the ink for ink-jets of the above-mentioned composition. It is characterized by a certain thing.

0022the ink cartridge concerning another embodiment of the present invention and ink -- Accommodate it sets to the ink cartridge provided with the To ink seat part -- above-mentioned Inc. -- the above-mentioned style It is ink for ink-jets of Formation.

0023inn in which the recording unit concerning another embodiment of the present invention and ink are stored the recording unit provided with the The seat part and the recording head for carrying out discharge of the ink -- it is -- above-mentioned Inc. is ink for ink-jets of the above-mentioned composition -- the feature It carries out.

0024An ink-jet recording device concerning another embodiment of the present invention, ink -- Yield Ink provided with A do to the ink seat part which carries out Capacity, and the record for carrying out discharge of the ink it sets to a jet recorder -- inn for ink-jets of the above-mentioned composition of above-mentioned Inc. It is The.

0025according to the present invention, it excels in color enhancement -- it has high surrounding gas-proof nature -- further -- Bron-proof Ink for Ink jets which gives the picture excellent in A nature can be provided. According to another embodiment of the present invention, the above-mentioned ink for ink-jets was used. An ink jet recording method, an ink cartridge, a recording unit, and in Cug A Tut recorder can be provided. Brief explanation of the drawings

0026Drawing 1, Baby square It is a measurement principle figure of the X-rays scattering-about method.

0027Drawing 2 -- baby square of a phthalocyanine system color material and a triphenylmethane series color material X ray Scatter It is a random profile.

0028Drawing 3 -- it is a key map of the distributed distance of the molecular aggregate of a phthalocyanine system color material. Drawing 4 is a perspective view of a recorder.

0029Drawing 5, It is a perspective view of the mechanism part of a recorder.

0030Drawing 6, It is a sectional view of a recorder.

0031Drawing 7, Perspective view showing the state of equipping a head cartridge with Ink evening An It is. '

0032In Drawing 8, it is an exploded perspective view of Doka 1 Toridge.

0033It is a front view showing the record element board in a Red card ridge to Drawing 9. The best form for inventing

0034the desirable embodiment of the present invention is listed to below -- it explains in detail.

0035In ink, salt is to ion the case where a color material is salt also in the present invention. It is a facilities top although it dissociates and exists, It is expressed as "salt is contained."

0036To ink >

0037Hereinafter, the ingredient etc. which constitute ink for ink-jets concerning the present invention (there is This only called ink hereafter) are described in detail.

0038Content of the compound denoted by the above-mentioned general formula (I), or its salt (mass %) Inn In many ink, it is easier to generate bronze to all the The mass than 3 .0 mass %. It is d especially._{7 5}A value is 7.5. When exceeding 0 n m, in bronze, a To generate . To case notably It is. Content of the compound denoted by the above-mentioned general formula (I), or its salt (mass %) Inn which is less than 3 .0 mass % exceeding 0 .5 mass % to all the ink mass Especially at The, it is d._{7 5}A value is 1. 0.6 When exceeding 0 n m, the case where bronze is generated It is. These artificers control generating of a title and a bronze phenomenon for these subjects. It is recognized as things being required and came to succeed in the present invention.

0039(Color material)

0040The ink concerning the present invention, the compound denoted by general formula (I), or its salt is contained. Carrying out is indispensable. the compound denoted by following general formula (I) or its salt has the hue of cyanogen -- phthalocyanine Invitation with the feature of excelling in surrounding gas-proof nature It is a conductor.

0041General formula (I)

0042<img file="WO2006011663A1_D0002.tif" />(-- General type (I) Inside and M being an alkaline metal or ammonium. R)₂They are a hydrogen atom, a sulfonic group, and a carboxyl group to Each one independence. (however, R)₂The same the case where it becomes a hydrogen atom is sometimes excluded -- it is -- Y -- chlorine atom, a hydroxyl machine, a Amino machine, and mono-or are dialkylamino groups -- 1, m, and n -- respectively -- 1 = 0*2, m=l*3, and n= l*3 (however, 1+m+n = 3*4) it is -- substitution machine A substitution position is only the 4th place or 4'.

0043Substitution machine [ in / unescapable / in / generally / the time of the composition / in a phthalocyanine derivative / a general formula (I V) ] R_n(n : :! Substitution position of * 16) (the position of the carbon atom on the Benzene core which Rt R^ combines is defined as 1 place * 16 place, respectively) Opposite-sex object It contains in many cases. however, the substitution position isomer of these and This usually distinguished mutually there is nothing -- it is regarded as the same derivative in many cases.

0044General formula (I V)

0045<img file="WO2006011663A1_D0003.tif" />The color material used in the present invention, a sulfonic group, and unreplaced sulfamoyl group (one S0)₂NH₂or -- about (R in general formula (I I I)) the 4th place and 4' [ in / for a substitution sulfamoyl group (basis denoted by a general formula (I V)) / general formula (I) ]₂R₃R₆R₇R₁₀Rn, R₁₄R₁₅it introduces alternatively -- it is the phthalocyanine derivative which set the substitution cardinal number to 3*4. These artificers and this compound are contained. The recorded matter obtained using ink finds out excelling in surrounding gas-proof nature extremely. It was.

0046composition of the compound denoted by general formula (I) used in the present invention, or its salt 4 -- To -- sulfo phthalic acid derivative, Or 4 -- a sulfo phthalic acid derivative -- and -- (-less water) Lid obtained by making a Off evening Le acid derivative react under existence of metallic compounds The Russia Nin compound is used for materials. A in the above-mentioned phthalocyanine compound It is amino under existence of organic Amin after changing a Luhon acid radical into a chlorosulfonic acid machine. It is obtained by making a-izing agent react.

0047General formula (V)

0048<img file="WO2006011663A1_D0004.tif" />It is Show below about the desirable example of substitution A ^ / Famoil machine denoted by general formula (V). To. of course, the substitution sulfamoyl group used for the present invention and the thing restricted to this it is not . The substitution sulfamoyl group denoted by general formula (V) and the form of free acid It is shown.

0049<img file="WO2006011663A1_D0005.tif" />With the compound which the above-mentioned illustration substitution machine 1 replaced (with i.e., the following general formula) (I I I) especially The compound expressed or its salt is most from the balance of the color enhancement and surrounding gas-proof nature. It is a desirable compound.

0050General formula (I I I)

0051<img file="WO2006011663A1_D0006.tif" />

0052(the inside of general formula (I I I) and M are an alkaline metal or ammonium, and 1, m, and n are 1 = 0*2, m= 1*3, and n=l*3, respectively (however, l+m+n = 3 4) -- the substitution position of a substitution machine is only the 4th place or 4'.)

0053however, it is used in the present invention -- "-- a substitution cardinal number like General type (I) is 3 or 4, i.e., 1+m+n = 3*4, -- and -- in the compound in which limitation of a substitution position was done at least at the 4th place and 4' the following table -- 1 and a table -- as [ show / in 2 ] -- sulfonic group which is a substitution machine replaced by a lid Russia 2 A frame (- SO)₃M), unreplaced Sulfamol machine (- SO)₂NH₂And substitution sulfamoyl group (it is expressed with general formula (V) and is To machine) Much opposite-sex objects in which numbers differ exist. the compound denoted by general formula (I) -- moreover -- the salt is a mixture of these opposite-sex objects -- the number of the opposite-sex objects, and difference in a kind Even if it is a compound of the same structure, it is checked that the characteristics differ greatly. ing. And the difference in the coherence which the color material itself has in one of the characteristics is mentioned. Table 1

0054Table 1: S3>> (place stand > of H"m+n=4) of Place * cardinal number, Place * machine position, and opposite-sex object

0055<img file="WO2006011663A1_D0007.tif" />Table 2

0056Table 2: Kind of substitution machine *, and g Conversion machine position and opposite-sex object (in case of l+m+n=3)

0057<img file="WO2006011663A1_D0008.tif" />

0058Being general, a phthalocyanine system color material, and color material of other structures (a truffe enyl meta- A system, a Azo system, a xanthene series, etc.) It compares and coherence is high. The above-mentioned coherence By raising, robustness also becomes high. On the other hand, they are a color material with high coherence, and ink. The coherence of the color material which can be set also becomes high. Therefore, it is a picture when it prints on a recording medium. There is a tendency for generating of the bronze phenomenon which causes deterioration of grace to become remarkable.

0059On the contrary, robustness, especially surrounding gas-proof nature are To declines the case where the coherence of a color material is remarkable and low. To. Therefore, the recorded matter obtained using the ink containing the above-mentioned color material and environment-proof The image keeping quality of yellow ink excellent in gas nature, Magenta, Inc., and the level is acquired. To may not be made.

0060therefore, generating of a bronze phenomenon can be controlled the case where the compound denoted by general formula (I) or its salt is used as a color material -- and desired surrounding gas-proof nature -- profit To be -- it is [ like ] necessary to control the coherence of a color material.

0061it is based on above-mentioned knowledge -- coherence of the compound denoted by general formula (I), or its salt Paying one's attention, these artificers inquired wholeheartedly. As a result, it is expressed with General type (I). It is changing the kind of substitution machine of the color material which is Compound or its salt, Condensation of a color material the Amin compound which controls collection nature and is further denoted by general formula (I I) -- inn according to making The contain, it excels in color enhancement -- controlling generating of a bronze phenomenon it can do -- and the method of improving surrounding gas-proof nature is found out -- it came to succeed in the present invention.

0062[Measurement of the coherence of a color material]

0063In measurement of the coherence of the color material used in the present invention, it is a baby square. The X-rays scattering-about method applies. It can do.

0064baby square The X-rays scattering-about method, The "newest colloid chemistry" (Kodansha scientific Fumio Kitahara, Furusawa Japanese national) And "surface state and colloidal state" (the Tokyo Kagaku Dojin Nakagaki positive happy) etc. -- it is indicated -- as Distance between the colloidal particles in a colloidal solution It is a technique used for calculation general-purpose.

0065baby square the outline of an X ray dispersion device -- baby square the figure which is a measurement principle figure of the X-rays scattering-about method -- using 1 Explanation is carried out. it generated from X line source X-rays -- the -- while passing along 1* The 3 slit, focal spot size is extracted to a grade of several millimeters or less -- sample solution is irradiated. In sample solution It glared. Imaging after being scattered about by the particles in X-rays and sample solution It is detected on a rate. it was scattered about X-rays -- the difference in the Optical path difference -- interference -- Cause since he is absorbed, zero acquired value is used -- the distance d value between particles is calculated by formula of B r a g g (account type [ of lower ] (1)). With d value calculated here and a constant interval It is considered the distance of a center to the center of the arranged particles. d = formula (1)

00662 sin (9

0067(As for the inside of a formula (1), and lambda, as for the wavelength of X-rays, and d, the distance between particles and 0 are scattering angles.) . -- the case where the particles in solution generally have not arranged regularly -- scattering angle profile eye A peak does not occur in Le. Color material used in the present invention (phthalocyanine system color material) In the case of solution 2 strong peak which has the maximum in the range of 0 = 0 ° *5 ° it is detected -- particles formed by condensation of a phthalocyanine system color material molecule (collection [ of molecules ] union) It can check having arranged under a certain fixed rule. To Drawing 2, it is following-ization. The triphenylmethane series color material which has the structure denoted by Compound (1), the phthalocyanine system color material which has the structure denoted by general formula (I), and each 1 0 mass % solution The scattering angle profile which can be set is shown. Color which has the hue of the cyanogen more nearly same than Drawing 2 Also in material, having a scattering angle peak specifically a phthalocyanine system color material It understands. That is, the case of a phthalocyanine system color material, in solution, some phthalocyanine molecules condense and it forms a molecular aggregate. And distance between molecular aggregates It has fixed distribution as shown by a scattering angle profile.

0068Compound (1)

0069<img file="WO2006011663A1_D0009.tif" />

0070Drawing 3 -- it is a key map of the distributed distance of the molecular aggregate of a phthalocyanine system color material. Figure They are r 1 and a molecule about the radius of the molecular aggregate of like and a certain phthalocyanine system color material shown in 3. Distance between aggregates is set to d 1. If the structure of a phthalocyanine system color material is the same If it assumes that The d l is always constant, a part for a phthalocyanine system color material to form it follows that the radius of a child aggregate becomes large with r l->r 2 -- baby square Measurement from the X-rays scattering-about method It is thought that constant d value carried out also becomes large to d 2 ->d 3. therefore, the above-mentioned method d value measured and index showing the size of the molecular aggregate of a phthalocyanine system color material it is -- it thinks -- the size of the molecular aggregate which a color material molecule forms, so that d value is large -- coming To is considered to be large intermediary To have. ，

0071Seki of d value in the ink containing a phthalocyanine system color material, and a bronze phenomenon When charge was questioned, it turned out that there is a tendency which a bronze phenomenon tends to generate, so that d value was large in the case of the lid mouth cyanine system color material shown with the same structural formula. It is To consider about a bronze phenomenon occurring by set of the color material molecule on a recording medium. Result which proves that To, and above-mentioned d value and the size of a molecular aggregate are correlated It became.

0072Distribution of the distance between the peak shape in a scattering angle profile and a molecular aggregate, i.e., distribution of the distributed distance of a molecular aggregate, is shown. Like and at this rate [ which were described above ] When Scattered distance considers that it is an index showing the size of a molecular aggregate, it is this scattering angle. It is Thought when distribution of the size of the molecular aggregate in a profile and solution is shown. It can obtain. That is, it is a part in solution about the peak area of a scattering angle profile. If it is considered as the size of the whole child aggregate, it will be Frequent of a molecular aggregate with it. There is a tendency which a bronze phenomenon tends to generate, so that a degree is high. [ large namely, d value and ] [ large ] Therefore, bronze expression It is [ reducing the frequency of a large molecular aggregate, and ] bronze expression that it is easy to generate an elephant. It is thought that generating of an elephant can be controlled. However, remarkable small molecule Although a bronze phenomenon becomes difficult to occur the case of the ink only containing an aggregate, the surrounding gas-proof nature will also fall. for this reason, generating of a bronze phenomenon can be controlled -- and -- from a viewpoint of obtaining surrounding gas-proof nature -- a molecular aggregate -- a large -- It is necessary to control Tears (size of d value) to Sure.

0073being general and the case where it has distribution by frequency with the size of a color material molecule -- man -- 100 -- In sight -- recognition It is referred to as 1Z4 of the threshold of the made vision limit, and its amount of whole. this , -- the big molecular aggregate which a bronze phenomenon tends to generate becomes 1Z4 or less [ of the whole ] a point and the small molecular aggregate which in other words a bronze phenomenon does not generate easily -- 3 of the whole d value of the point which becomes four or more -- d_{7 5}It is considered as a value and is the d._{7 5}it is control to the specific range about a value generating of a bronze phenomenon is controlled by carrying out -- inn which has high surrounding gas-proof nature It becomes possible to obtain The.

0074d actually computed from the peak of 20 values in a scattering angle profile_peakA value and above-mentioned d₇₅It is d when the correlativity of a value and the generating level of a bronze phenomenon was investigated._peakd which took into consideration the distribution factor of the size of the whole molecular aggregate rather than the value₇₅Direction of a value It became clear that correlativity with a bronze phenomenon was high. Be at the time of calculating 20 values - A line is pulled in [ 0.5 " ] * 5 degrees.

0075the compound denoted by general formula (I) which is a phthalocyanine system color material, or its salt -- it is -- the compound to which the number, kind, and substitution position of the substitution machine were changed, i.e., coherence, -- Co The following [ it uses the color material which carried out Troll ] experimented. inn containing the above-mentioned color material The is prepared -- measuring the scattering angle profile of the ink -- d₇₅The value was computed. Next, obtained d₇₅The coherence of the color material of a value to each was evaluated. As a result, the above-mentioned d₇₅a value is below 6. 70 or more nm 10. 60 nm -- content of a color material (the amount % of nature ) A bronze phenomenon is generating when exceeding 3. 0 mass % to all the ink mass. It carries out. The above-mentioned d₇₅a value exceeds 10. 6 Onm -- when the content of a color material exceeds 0. 5 mass % , a bronze phenomenon occurs.

0076in which [ of the above ] case, it also sets -- the Amin compound denoted by a general formula (I I) -- inn generating of a bronze phenomenon is controlled by making The contain -- high surrounding gas-proof nature Having was found out.

0077Baby square Fixed [ case where d value is measured by the X-rays scattering-about method ] in the molecule density in solution It is necessary to carry out. For this reason, d value is measured in the ink which fixed color material concentration. Things are preferred. it sets to the present invention -- content of a color material (mass %) Quality of all [ ink ] it diluted using pure water so that it might become 0. 5 mass % to quantity -- Dilution, Inc. -- an opposite -- It carried out and measured the scattering angle profile. Absorbance at the time of diluting that the content of the color material in ink is 0. 5 mass %, and the ink with pure water 150 times It is possible to verify by When which is the range of 1.15*1.30. The measurement conditions of Absorbance are shown below. spectrum photometer: the account of self--- a spectrum -- photometer (brand name: made by U-3300; Hitachi) Measurement cell: 1 cm quartz cell

0078Sampling interval: 0. 1 nm

0079Scanning speed: 30 nm/m i n

0080Measurement count: 5 times measurement average

0081maximal absorption wavelength [ in / in the coherence of the color material described above / an absorption spectrum ] (lambda max) Both -- there is correlativity. Molecular association nature is high. (d)₇₅The tendency for lambdapiiota a x to be as low as high ink has a value. Therefore, d₇₅it correlates with a value lambda ma X is used -- color material It is also possible to evaluate coherence. in this case -- using pure water -- 2000 times . -- it can set in the diluted ink and ma X is less than 612. 0 nm -- content (mass %) of a color material If 3. 0 mass % is exceeded to all the ink mass, a bronze phenomenon will occur. Above-mentioned Am a X is less than 608. 0 nm, and a bronze phenomenon occurs the case where the content of a color material exceeds 0. 5 mass %. Measurement condition of a maximal absorption wavelength It is the same as that of an affair and the measurement conditions of above-mentioned Absorbance.

0082in which [ of the above ] case, it also sets -- the Amin compound denoted by general formula (I I) -- inn generating of a bronze phenomenon is controlled by making The contain -- high surrounding gas-proof nature Having was found out.

0083[A verification method of a color material]

0084Illustration compound 1 (the compound denoted by a general formula (I I I), or its salt) which is an example of the color material used in the present invention The following (1) which used high-speed-liquid-chromatography (H PLC) for verification * The verification method of (3) is applicable.

0085(1) Retention time of a peak

0086(2) The maximal absorption wavelength in the peak of (1)

0087(3) MZZ (po s i) of the mass spectrum in the peak of (1)

0088The analysis conditions of high speed liquid chromatography are as being shown below. as opposed to the ink solution diluted with pure water to a 50 times as much abbreviation -- the following conditions -- high-speed liquid chromatograph analysis by Í 1 is conducted -- retention time of a main peak (r e t e n t i on t im e) and the maximal absorption wavelength of a peak are measured.

0089* Column: S ymme t r y C I 8 2. 1 mmx 1 50 mm

0090. Column temperature: 40

0091. Flow velocity: 0. 2m 1 / m i n

0092* PDA: 210 nm*700 Gene

0093* A mobile phase and gradient conditions : Table 3 table 3<img file="WO2006011663A1_D0010.tif" />The analysis conditions of a mass spectrum are as being shown below. At the obtained peak It receives, a mass spectrum is measured on condition of the following, and it is To measure about MZZ (p o s i). To.

0094. The ionizing method

0095* ES I Cavilary voltage 3. 1 k V

0096Deliquoring gas 300

0097Ion source temperature 120V

0098* the retention time to detector po s i 40 V 500-2000 amu / 0. 9 s e c illustration compound 1, a maximal absorption wavelength, and the value of MZZ -- a table -- it is shown in 4. If it corresponds to the compound used in the present invention the case where it corresponds to the value shown in Table 4 It can judge. it sets to the color material used for the present invention -- High speed liquid chromatography -- (HPLC) the peak ratio of the mass spectrum obtained from a peak, and a color material -- Different by the mixing ratio of the opposite-sex object in which the number, kind, and substitution position of the substitution machine to kick differ from each other To, the following table -- the feature that the peak of MZZ indicated to 4 is always detected -- an owner -- It carries out. Therefore, the verification method of this color material and ink contain the color material used for the present invention. It is an effective means as a method of verifying whether it carrying out. Table 4<img file="WO2006011663A1_D0011.tif" />

0099(Amin compound denoted by general formula (I I))

0100It is To contain about the Amin compound expressed with the following general formula (I I) by the ink of the present invention. To is indispensable.

0101General formula (I I)

0102<img file="WO2006011663A1_D0012.tif" />

0103Inside of a General type (I I), R R₂R₃A hydrogen atom, a Alkyl machine, a hydroxy low-grade Alkyl machine, a cyclohexyl machine, and mono-or are a Dialkylamino alkyl machine, a Shano low-grade Alkyl machine, and a phenyl group that may be replaced at Are independence (however).

0104R_1*R₂R₃The case where All serves as a hydrogen atom is excluded.

0105Especially by the thing made for ink to contain the Amin compound denoted by the above-mentioned general formula (I I), the effect which controls a bronze phenomenon is acquired notably. this reason and ink -- With it sets on the recording medium which supported -- the case where evaporation of a water-soluble organic compound takes place -- the following It thinks for a phenomenon [ like ] to happen. Amin combination denoted by general formula (I I) When a thing exists, the unshared electron pair of the nitrogen atom in a Amin compound is lid Russia 2. The primary condensation object and interaction of a A system color material are started. A Amin compound is the circumference of a condensation object. Since steric exclusion will be encountered if it exists, secondary condensation becomes difficult to take place.

0106nitrogen field with the interaction of a Amin compound and a primary condensation object, and an unshared electron pair in order that a child may approach a primary condensation object easily -- as a Amin compound -- primary amine -- business when it is, it happens most effectively -- it ranks next -- the order of the second class Amin and the third class Amin -- effect It is thought that it is obtained. a Amin compound and a primary condensation object carry out an interaction a case -- a Amin compound -- if an organic group is bulky, primary condensation objects cannot approach easily a sake -- secondary condensation -- happening -- being hard -- thinking -- having . a Amin compound -- high-boiling it is more desirable than a point -- setting on a recording medium, when it is a solid at normal temperature -- organic compound since it is easy to stop near the primary condensation object, without evaporating -- secondary Condensation A collection does not happen easily.

0107it is based on above-mentioned knowledge -- the result in which these artificers inquired wholeheartedly -- sex with high coherence The compound or That denoted by general formula (I) which has quality, and which is a phthalocyanine system color material Salt, by using combining amine^Compound denoted by a general formula (I I), secondary condensation of the color material on a recording medium is controlled exactly -- bronze phenomenon generating can be controlled -- having high surrounding gas-proof nature was found out. especially tris (hydroxymethyl) Amino methane is first-class Amin especially -- it has a bulky tris hydroxymethyl group in the molecular structure -- further -- normal temperature -- solid It is. for this reason, the compound denoted by general formula (I) from a viewpoint expressed above -- or -- The Pronz phenomenon of that salt can be controlled very effectively.

0108Content of a Amin compound denoted by general formula (I I) (mass %) Quality of all [ ink ] More than 0 .1 mass % is 1 to quantity. It is preferred that it is 0 .0 mass %. Content The bronze prevention effect may become insufficient and aggravation of dischargeability may arise [ case where it is less than this range ] depending on the ink-jet recording device to be used the case where there is more content than this range. Amin combination denoted by general formula (I I) Content of a thing (mass %) Color which is a compound denoted by general formula (I), or its salt Content of material (mass %) It receives and it is preferred that it is more than 5 .0 %. Content The effect which controls generating of a bronze phenomenon as a ratio is less than 5 .0 % demonstrates enough. l It is because it may not be. Amin compound denoted by general formula (I I) Content (mass %) Color material which is a compound denoted by general formula (I), or its salt Content (mass %) It receives and is 1. 0 0 It is preferred that it is below 0 %. The ratio of content is 1. 0 0 If 0 % is exceeded, dischargeability depending on an ink-jet recording device It is because it may get worse. Amin compound denoted by general formula (I I) If it is made to contain too much, generating of a bronze phenomenon can be controlled, but the viscosity of ink Since it may become high, dischargeability may be affected.

0109(Water medium)

0110amine-izing denoted by general formula (I I) described by the ink constituent of the present invention, and the above the effect by adding these other than Compound is acquired -- and the object of the present invention It is a range which does not spoil an effect. With the mixed solvent of water or water, and various water-soluble organic solvents A certain water medium can be used.

0111if it is a water-soluble organic solvent and water solubility, there will be no restriction in particular -- ethanol, Iso pro Panol, n -- Butanol, Isobu evening Knoll, and the second butanol, third Butano 1 Alkyl alcohol of carbon numbers 1*4, such as Le; N and N -- Dimethylform amide -- moreover -- N and N -- carboxylic amide; acetone, such as Dimethylaceto amide, Methyl ketone and 2 -- Methyl 2 -- Ke . tons, such as hydroxy pentane 4 1 ON, Or keto alcohol; cyclic ether, such as a tetrahydro franc and dioxane; Glycerin, Ethylene glycol, diethylene glycol, and Triethylene glycol - Le, Tetraethylene glycol, 1, 2 or 1, 3 -- Propylene glycol, 1 2 or 1, 4 -- Butylene Glycol and Polyethylene Glycols, 1 3 The All [ Tangji ], 1, 5 -- Pentanediol, 1, 2 -- Hexanediol 1 6 [ Oar, 1, 2 6 -- Xan Triol and Acetylene Glycol Derivative, ] -- Hexanediol, Dithioda Recall, and 2 -- Methyl 1 and 3 -- A □ Pansy Polyhydric alcohol, such as Trimethi roll propane; mono-[ ethylene glycol ] Methyl (or Ethyl) Ether, Diethylene glycol monomethyl (or Ethyl) ether and triethylene glycol monoethyl (or butyl) Ether etc. Alkyl ether of polyhydric alcohol; 2 -- Pylori boss, N -- a methyl 2_pylori boss, 1, and 3 -- Dimethyl_2 Imidazolidinone and N -- -- methyl Morpholi heterocycles;, such as A, -- sulphur-containing compounds;, such as dimethyl sulfoxide, -- urea and urea A derivative can be used. even if it uses by the above-mentioned water-soluble organic solvent and independent -- Some -- It may use as a mixture.

0112More than 5 .0 mass % is 9 preferably to the content of these water-soluble organic solvents, and all the Ink mass. More preferably than below 0 .0 mass %, it is 1. More than 0 .0 mass % is 5. It is below 0 .0 mass %. the case where content is less than this range -- object for ink-jets reliability, such as dischargeability at the time of using as ink, may get worse -- content Ink supply is [ case where it is more than this range ] poor when the viscosity of Ink rises. It is because it may occur.

0113Water is deionized water. (ion exchange water) Using is preferred. Content of water It is 1 to all the ink mass. More than 0 .0 mass % is 9. It is below 0 .0 mass %. It is desirable.

0114If it sets to the present invention, it is 2 also in the above-mentioned water-soluble organic solvent. -- Pylori boss, Poly Ethylene glycol (more than molecular weight 2 0 0) and triethylene glycol Monoje Alkyl ether of polyhydric alcohol, such as Ruetel general formula (I) -- a table -- Effect which controls generating of a bronze phenomenon the case where it uses together with a To be compound or its salt For a certain reason, it is desirable. In particular, it is 2. -- Combination denoted by pylori boss and general formula (I) Effect which controls generating of a Pronz phenomenon effectively especially the case where it uses together with a thing or its salt Since there is Result, it is desirable.

0115These specific water solubility organic solvents can control generating of a bronze phenomenon. Although a To mechanism is not clearly clear, it is guessed as follows. Ink Baby square d by the X-rays scattering-about method_{7 5}These specific water solubility [ value ] organicity in ink It does not change depending on the existence of a solvent. these specific water solubility Organic dissolution from this the coherence of the color material in the inside of an agent and ink is not necessarily changed -- smelling on a recording medium It is thought that it is because condensation of The and the molecular aggregate comrade of a color material can be controlled. It is the above-mentioned effect by making ink contain these specific water solubility organic solvents. The content (the amount % of nature ) of these specific water solubility organic solvents in ink in order to obtain is 5 to the content (mass %) of a color material. It is preferred that it is more than 0 %. (Other additive agents)

0116Necessity is accepted in the present invention and they are a P H adjustment agent, a surface-active agent, a Prevention * agent, an antiseptic, an antifungal agent, a chelation agent, a Prevention * agent, an ultraviolet ray absorbent, a viscosity controlling agent, and Defoaming. An agent water-soluble polymer, etc. and various additive agents may be made to contain.

0117case p H of the compound denoted by general formula (I) or its salt, and ink is low -- inn the solubility to The falls -- condensation takes place easily. therefore, p H of ink -- high -- There and condensation are controlled -- it becomes difficult to generate a bronze phenomenon. For this reason, p H of ink is 6.0*1. The range of 1.0 is preferred. It is an effect especially about a bronze phenomenon. It is good Up that p H of ink is especially 9.0 or more in order to control in Result. It is by carrying out and is ..

0118p H of a rho- eta adjustment agent and ink -- 6.0*1 It is a thing controllable in the range of 1.0. with -- there is no restriction in particular -- concrete For example, Diethanolamine and Tori Etah Alcohol compounds, such as no Ramen and iso propanolamine; water oxidization Lithium, Hydroxide of the Al power Li metal, such as water oxidization power Rum; carbonate of alkaline metals, such as ammonium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate, etc. It is mentioned. Diethanolamine, Triethanolamine, and an iso pro especially An effect is Ah also to control of carbonate of the Al power Li metal, such as Alcohol compounds, such as Panormin, lithium carbonate, sodium carbonate, and carbonic acid power Rum, and a bronze phenomenon. It is [ especially To sake ] desirable.

0119The example of a surface-active agent, a Anon surface-active agent, a double-sided surface-active agent, and cation community A field active agent, a nonionic-surface-active agent, etc. are mentioned.

0120The example of a Anon surface-active agent, Alpus Grus carboxylate salt, and alpha -- Talent reflex In sulfonic acid salt, Polyoxyethylene-alkyl-ether acetate and nu -- Acacia Amino acid and its salt, nu -- Acacia methyl taurine salt and alkyl sulfate Polio Sial kill ethereal sulfate salt, Alkyl sulfate polyoxy ethylene Alkaline The Tell phosphate and rosin Acid stone* Castor oil sulfate ester salt and lauryl alcohol Sulfur It is Xylos to acid ester salt, Alkyl phenol type phosphoric acid ester, Alkyl type phosphoric acid ester, Alkyl aryl sulfone chloride, Jetyl sulfo succinic acid salt, and Jetyl. Ruho succinic acid Geocchil sulfo succinic acid salt etc. are mentioned.

0121The example of a cation surface-active agent, and 2 -- A vinyl pyridine derivative and poly 4-Bini There are a kana lysine derivative etc. As a double-sided active agent, it is lauryl dimethylamino vinegar. Acid Tyne and 2 [ -- Hydronalium Kishacheye / Midazolinum solid in, ] -- Al kill--N -- Carboxyl methyl N palm-oil-fatty-acid amide propyl dimethylamino Acetic acid evening in and poliomyelitis Kuchil poly aminoethyl Grishin -- in addition to this -- imidazoline derivative etc. -- it is.

0122The example of a nonionic-surface-active agent, and Poli-kischelenno nil phenyl Aether, Polyoxy Ethylene octopus^" Rufue nil ether and polyoxy Ethylenedo de Sylphe nil ether, Polyoxy ethylene lauryl ether and poliomyelitis Kishilleno Rail ether, Polyoxyethylene alkyl ether and polyoxy Ether systems, such as Allyl kill alkyl ether, Polyoxy Ethylene Forein acid and polyoxy Ethylene Forein acid ester, Polyoxy ethylene distearic acid Ester and the Sorby evening Nerau rate, Sorbitan monostearate and the Sorby evening Monooree 1 A and sorbitansesquiolate, Ester systems, such as Polyoxy ethylene Monooree - A and polyoxy ethylene stearate, 2 4, 7, 9 -- Te Tiger Methyl 5 -- Crepe De Chine 4 and 7 -- Diol, 3 6 -- Dimethyl-- 4 -- Octin-- 3 and 6 -- Diol, 3 5 -- Dimethyl 1 Cetylene Glycol System (for example, Kawaken Fine Chemicals Hassetrienol E H and Nissin Chemical Sir Finnor 1 0 4) -- Key Scene 3 -- A, Such as Oar 8 2 and 4 6 5, Orfine S T G, etc. are Behavior. To be.

0123Organic nitrogen sulfur system, the example, for example, the organic sulfur system, of antiseptic and an antifungal agent, Organicity A halogen system, a Haloaryl sulfone series, and Ode propargyl system, N -- Haloalkyl A Chi system, a Benz thia Sole system, and Nito-thyl system, A pyridine system and 8 -- Talent Kisinari A A system and benzothia Sole system, An iso thiazoline system, a dithiol series, and Pyridine key The Cyd system and nitropropane system, An organic tin series, a phenol system, the 4th ammonium salt A system, a ♪ . rear gin system, a thia diazine system, a Ananilide system, a Addamantan system, and Ziqio power -- A Bamite system, the Blom-ized Inn Danone system, a Benzylb ROM acetate system, and mineral salt Compounds, such as a system, are mentioned.

0124An organic halogen system compound, for example, Penta chlorophenol sodium, is Behavior. Lifestyles and Pyridoxide system compound, For example, .2 -- Pyridinech all 1 Oxa -- an id -- sodium is mentioned -- a mineral salt system compound, for example, acetic anhydride soda it is mentioned -- iso thiazoline compound, For example, 1, 2 -- Benz iso thiazoline -- Three -- ON, 2_n [ -- Okthiru 4 1 iso thiazoline 3 ] [ -- ON, ] 5 -- Cros Mouth - 2_Methyl 4 -- Iso Thiazoline 3 -- ON, 5 -- the Cros mouth -- 2 -- methyl 4 2 -- -- iso thiazoline 1 -- 3 -- on-magnesium chloride and 5 -- the Cros mouth 1 -- Methi Roux 4 -- iso thiazoline 3 -- on-calcium chloride etc. are mentioned. As an example of other antiseptic and antifungal agents, it is sorbic acid soda benzoic acid Satellite. Pro cheating on the fare G X L made from Beam, for example, Abese, etc. (S), pro cheating on the fare X L -- 2 (S) etc. are mentioned.

0125'

0126A Curette-ized agent, for example, sodium acid citrate, and Ethylenediaminetetraacetic acid Na Thorium, Ninitro triacetic acid sodium, and hydroxyethyl ethylene diamine 3 Acetic acid sodium, diethylenetriamine pentaacetic acid sodium, and Uramil 2 acetic-acid Na Thorium etc. are mentioned.

0127a Prevention * agent, for example, acid sulfite salt, sodium subsulfite, and thioglycolic acid Ammonium, Diisopropyl ammonium night rye ♪, and 4 nitric-acid pen evening Eli a pickpocket -- a Xyl ammonium nightlight etc. are mentioned to 1^1 Le and Dicyclo. An ultraviolet ray absorbent, for example, a benzophenone series compound, and benzotriazole series A compound, a cinnamic acid system compound, triazine compound, and stilbene compound, or -- Conversion which absorbs the ultraviolet rays represented by the benzoxazole system compound, and shows a fluorescence Compound and what is called a fluorescent brightener can also be used.

0128A water-soluble high molecular compound other than a viscosity controlling agent and the water-soluble organic solvent is mentioned, for example, they are polyvinyl alcohol, a cellulose derivative, polyamine, the poly imine, etc. It is mentioned.

0129An antifoaming agent, a fluorine system, and a silicone series compound are used if needed.

0130<Recording medium>

0131It is With about the recording medium used when forming a picture using the ink of the present invention, and ink. Anything can be used if it is a recording medium which records by supporting. the vesicular structure in an ink absorbing layer is formed for color materials, such as the present invention and color material pigment, -- fine -- it is made to stick to particles -- record in which a picture is formed at least from this particulate to which it stuck it is applied to a medium -- it is suitable especially when using the ink-jet method. This Yo The sky where the Something recording medium for ink-jets was formed in the ink absorbing layer on a Support^object It is preferred that it is what is called an absorption type that absorbs ink according to spare time.

0132let an absorption type ink absorbing layer and particulates be subjects -- necessity is accepted -- binder It is constituted as a porous layer containing the additive agent of 1 or others. The example of particulates, silica, clay, talc, and calcium carbonate, kaolin, alumina, or Al Inorganic pigments and urea formalin resin, such as aluminum oxides, such as the Mina hydrate, diatomite, titanium oxide, hydro-Tulsai, and a zinc oxide, ethylene resin, styrene resin, etc. an organic color is mentioned -- these one or more sorts are used. as a binder -- good -- Water-soluble polymers and latex can be mentioned to what is used for Suitable. To. For example, polyvinyl alcohol or its denaturation object, starch, or its denaturation object, Gelatin or its denaturation object, gum arabic, and carboxymethyl cellulose, To' Dollo Cell mouths 1, such as Xeechil cellulose and hydroxy pro oil methyl cellulose A derivative, S B R latex, N B R latex, and methyl methacrylate 1 The Evening diene copolymerization object latex, Functional group denaturation polymer latex and ethylene acetic acid Bipinil system copolymer latex, such as a nil copolymer, Polyvinyl pyrrolidone and anhydrous Maleic acid or its copolymer, an acrylic ester copolymer, etc. are used, and it can use combining two or more sorts if needed. in addition, an additive agent -- Use can also be carried out -- for example, -- accepting necessity -- a dispersing agent, a thickener, and a pH adjuster -- lubricous An agent, a fluid denaturing agent, a surface-active agent, an antifoaming agent, a release agent, a fluorescent brightener, an ultraviolet ray absorbent, an antioxidant, etc. are used.

0133In particular, the recording medium preferably used in the present invention and the recording medium which formed the ink absorbing layer for the particulates whose mean particle sizes are below l^m as a subject are preferred. The example of the above-mentioned particulates, the Thilly power particulates, aluminum oxide particulates, etc. are mentioned. To. desirable as a silica particle -- it has trouble -- Thilly represented by colloidal silica They are power particulates. Although colloidal silica itself is more nearly available than a market, what was published at Patent No. 2803134 and the No. 2881847 gazette especially It is desirable. A thing desirable as oxidization aluminum particulates, alumina hydrate particulates, etc. It is. Aluminum expressed by a following formula as one of such the alumina system paints A Na hydrate can be mentioned.

0134A 1₂0₃__n(OH)_2n'mH₂O

0135n expresses any of the integer of 1, 2, or 3 they are among the above-mentioned formula -- m -- 0*10 -- good -- better -- To expresses the value of 0*5. However, m and n are not simultaneously set to 0. mH₂In the case of 0 and many, it is mH.₂Thing also showing the aqueous phase which does not participate in formation of zero crystalline lattice and which can be Desorptioned For a certain reason, m can also take the value which is not an integer or an integer. This kind of material When Desolation is carried out, m may reach the value of 0.

0136An alumina hydrate, U.S. Pat. 4, 242, No. 271, U.S. Pat. 4, and 20 2, hydrolysis of aluminum Alkoxide of a statement of No. 870, The Al Min acid Nato Hydrolysis of Rum, and Japanese Patent Publication No. 57 -- The Al Min acid Na given in 44^No. 05 gazette Solution, such as sodium sulfate and an aluminium chloride, is added to solution, such as thorium. It can manufacture by the method of neutralizing, etc. and a publicly known method. Having a base material for supporting the above-mentioned ink absorbing layer a recording medium It is desirable. a base material and an ink absorbing layer are the above -- forming by porous particulates It can be possible and can convey according to conveyance mechanisms, such as an ink-jet printer. if stiffness is given, there will be no restriction in particular -- anything can be used. Are concrete, for example, Wadding which comprises a pulp raw material by making a natural cellulose fiber into a subject. Possession object, polyester (example: polyethylene tele phthalate) and cellulose -- doria Csete 1 ♪, polycarbonate, polyvinyl chloride, polypropylene, and polyimide etc. -- at least 1 side of the plastic support which consists of materials, and a base paper -- white pigment etc. Resin-coated paper which has the added resin coating layer-ed [ polyolefin resin ] (example: R C Bex par) It is mentioned.

0137Tooth ink Jet recording method>

0138Inge concerning the present invention, and the process of carrying out discharge of the ink with an inkjet method -- an owner -- Especially the thing used for the ink jet recording method to carry out is preferred. Ink Jeetsu ♪ Record which makes dynamic energy act on a record method and ink, and makes ink breathe out A method, record method which makes thermal energy act on ink and makes ink breathe out, etc. It is. Account of an ink-jet which exploits thermal energy in the present invention especially Recording method can be used preferably.

0139<Ink cartridge>

0140Suitable Ink cartridge to record using Ink concerning the present invention The ink cartridge provided with the ink seat part which stores the ink of these is Behavior. To be.

0141<Recording unit>

0142a suitable recording unit to record using the ink concerning the present invention, and this , -- the ink seat part which stores ink, and record Uny ♪ provided with A do to record It is mentioned. the thermal energy especially corresponding to a record signal in the above-mentioned recording head -- Í it is made to act on An -- record Uny ♪ which generates a liquid ink drop by the above-mentioned energy It is mentioned.

0143Tooth ink-jet recording device>

0144a suitable recorder to record using the ink concerning the present invention -- these -- To the indoor ink of A do, it is record in the record which has an ink seat part in which ink is stored. the thermal energy corresponding to a signal is given -- it is generating about a liquid ink drop by the above-mentioned energy The device to carry out is mentioned.

0145Below, the schematic structure of the mechanism part of an ink-jet recording device is explained. Recorder a main part protects the role of each mechanism to a feeding part, a paper carrying part, a carriage part, a delivery unit, a chestnut 1 Ning part, and these -- it comprises an armoring part which gives design nature. Hereinafter, the outline of these is explained.

0146Drawing 4, It is a perspective view of a recorder. Drawing 5 and a figure -- 6 and the main part of a recorder -- inner -- it is a figure for explaining a part mechanism -- Drawing 5 -- the perspective view from an upper right portion, and Drawing 6 -- Recording The sectional side elevation of Specimen body is shown, respectively.

0147When feeding paper in a recorder, it is paper feed tray M 2 first. 0 6 0 is included. Paper In a part, only the number of predetermined leaves of a recording medium is feed roller M 2. 0 8 0 and separation roller 2 0 4 It is sent to the nip part which comprises 1. the sent recording medium -- nip part it dissociates -- only the top recording medium is conveyed. record intermediation sent to the paper carrying part The body and pinch roller holder M 3 0 0 0 and paper guide flapper M 3 0 3 it shows around 0 -- conveyance roller M 3 0 6 0 and pinch roller M 3 0 7 Roller of 0 It is sent to a pair. conveyance roller M 3 0 6 0 and pinch roller M 3 0 7 a La [ The mouth which consists of 0 - ] pair -- L F mho evening E 0 0 0 it rotates by the drive of 2 -- this rotation -- record a medium -- platen M 3 0 4 0 tops are conveyed.

0148the case where a picture is formed in a recording medium in a carriage part -- record -- A do H 1 0 0 1 (figure 7) it is made to arrange in the target image formation position -- electric substrate E 0 0 1 Signal from 4 Therefore, discharge of the ink is carried out to a recording medium. It is A do H I 0 to record. 0 About 1 Although detailed composition is mentioned below, It is A do H I 0 to record. 0 It is Care while recording by 1. Ridge M 4 0 0 Record main scan which 0 scans to a column direction, Conveyance roller M 3 0 6 By repeating by turns the subscan by which a recording medium is conveyed by 0 for whereabouts, it has composition which forms the picture on the recording medium.

0149It is delivery roller M 3 of The 1 at the recording medium which had the picture finally formed, and a delivery unit. 1 1 0 and spur M3 1 2 It is inserted into 2 A of 0, it is conveyed, and is delivery tray M 3. 1 6 It is Drain to 0. It is taken out.

0150it sets to a cleaning part -- the record before and behind image recording -- A do H 1 0 0 1 -- chestnut The object of Tongue(ing) 12 times sake, Cap M 5 0 1 It is 0 to record A do H 1 0 0 Í of 1 At *^voice stuck to the An discharge mouth, it is pump M 5. 0 0 When 0 is made to act, it is List to record. Do H 1 0 0 Unnecessary ink etc. are attracted from 1. Cap M 5 0 1 Where 0 is opened, it is cap M 5. 0 1 The ink which remains in 0 is attracted. By carrying out, it is Arrangement so that the adherence by Remaining, Inc. and subsequent evil may not happen. Consideration is carried out.

0151(Recording head composition)

0152Head cartridge H I 0 0 The composition of 0 is explained. Head car TRIZ H I 00 It is A do H I 0 to 0 and record. 0 1, ink tank H I 9 0 0 -- Means to mount and ink tank H 1 9 0 In order to supply ink to record from 0 at A do it has a means -- carriage M 4 0 0 It is removably carried to 0. Drawing 7 -- head cartridge H I 00 as opposed to 0 -- ink Tongue H I 9 0 It is a figure showing signs that it equips with 0. a recorder forms a picture by a yellow, the Mazen evening, cyanogen, black, the light Mazen evening, light cyanogen, and Green, Inc. -- ink tank H 1 [ therefore, ] 9 0 Seven classification by color is prepared independently also 0. The above-mentioned smell The ink concerning the present invention is used for The and at least one sort of ink. And like and each which are shown in a figure pass, and it is Red card ridge H 1. 0 0 It can detach and attach freely to 0. Ink tank H 1 9 0 Attachment and detachment of 0, and carriage M 4 0 0 0 Red card ridge H I 0 0 Intermediary To have [ as ] which can be performed in the state [ have ] where 0 carries. To Drawing 8, the exploded perspective view of Red card ridge H 1000 is shown. a figure -- setting -- head cartridge HI 000, The 1st record element board H 110 0 and The Record element board H 1101 of 2, the plate of The 1 H From 1200, 2nd A, and rate HI 400, electric wiring board HI 300, tank holder 1HI 500, passages forming member HI 600, filter HI 700, and seal rubber H 1800 grade It is constituted.

0153the 1st record element board H 1 100 and record element board H 1 of The 2 101 is a S i board -- a plurality of record elements for carrying out discharge of the ink to the one side (nozzle) It is formed by photolithography. A 1 grade which supplies electric power to each record element it is formed by electric wiring and membrane formation art -- plurality corresponding to each record element The ink channel is also formed by photolithographic technique. the Ink feed opening for supplying ink to a plurality of ink channels carries out an opening to the back It is formed for obtaining.

0154Drawing 9 is the 1st record element board H 1. It is a front enlarged drawing for explaining the composition of record element board H 1101 of 100 and The 2. H 2000*H 2600, it Soul sequence H which is a sequence (henceforth a nozzle sequence) of the record element corresponding to a Different ink color and by which Yellow, Inc. is supplied to the 1st record element board HI 100

0155Nozzle sequence H2100 to which 2000 and Magenta, Inc. are supplied, and cyanogen in The nozzle sequence of three classification by color of nozzle sequence H 2200 to which The is supplied is constituted. Nozzle sequence H 2 by which light Cyanink is supplied to the 2nd record element board H 1101

0156Nozzle sequence H2400 to which 300 and Black, Inc. are supplied, and Orange, Inc. The nozzle sequence of 4 classification by color of nozzle sequence H 2500 supplied and nozzle sequence H2600 to which light Mazen evening ink is supplied is constituted.

0157It is constituted by 768 nozzles located in a line in each nozzle sequence and the conveyance direction of a recording medium at intervals of 1200dp i (do t/i nc h; reference value), and is about 2 pico liters. An ink droplet is made to breathe out. the opening area in each nozzle discharge mouth -- about -- square [ 100 ] / zm²It is alike and is set up. the 1st record element board HI 100 and The 2 adhesion fixation of record element board HI 101 is carried out the 1st plate HI 200 -- here Ink feed opening H 1201 for supplying ink to record element board HI 100 of The 1 and record element board HI 101 of The 2 are formed.

0158plate H 1 of The 2 which has an opening in the 1st plate HI 200 adhesion fixation of 400 is carried out -- plate H 1400 of this The 2, electric wiring machine Record element board H 1 of board H 1300 and The 1 100 and record element board H 1 of The 2 as [ connect / 101 / electrically ] -- holding electric wiring board HI 300 To.

0159Electric wiring board H 1300 are the 1st record element board H 1. 100 and record of The 2 Element board H 1 In order to carry out discharge of the Ink from each nozzle currently formed in 101 An electric signal is impressed, The 1st record element board HI 100 and account of The 2 It locates and records on this electric wiring end part with the electric wiring corresponding to Recording element board HI 101. External signal input terminal H 1301 for receiving the electric signal from the main part of a device It has. The back of external signal input terminal H 1301 and tank holder 1 HI 500 Positioning fixation is carried out at the field side.

0160Tank holder H 1500 which, on the other hand, hold ink tank HI 900, passages forming member HI600 is fixed by for example, ultrasonic welding -- ink tank H -- ink channel H 1501 which lead to plate H 1200 of The 1 from 1900 -- form It has accomplished.

0161ink tank of ink channel H 1501 which engage with ink tank H I 900 filter H 1700 are provided in the side edge part -- invasion of the dust from the outside Intermediary To have [ as ] which can be prevented. moreover -- engagement part of ink tank HI 900 it is equipped with seal rubber HI 800 -- evaporation of the ink from an engagement part can be prevented obtaining -- intermediary To have.

0162It is tank holder one H1 as mentioned above. 500, passages forming member H I 600 Filter one H1 7 0 0 and seal rubber H 1 8 0 Tongue Khoul which comprises 0 Da part, Record element board H 1 of The 1 1 0 0 and The Record element board H 1 of 2 1 0 The 1 and 1st plate H I 2 0 0 and electric wiring board H I 3 0 0 and plate H I 4 of The 2 0 Record head part H I 00 which comprises 0 1, It joins together by adhesion etc. Head cartridge H 1 0 0 0 is constituted.

0163An electric signal is embraced as one form of a recording head here, and it is ink about film boiling. Electric heat conversion object which receives and generates the thermal energy for making it produce (record element) Bubble jet which records by using (registered trademark) It is 1 about the recording head of a method. The example was given and described.

0164About this typical composition and principle, it is U.S. Pat. 4 and 7. 2 3 and 1 2 No. 9 specification, the The 4, and 7 4 0 and 7 9 Fundamental principle currently indicated by No. 6 specification What is performed by using is preferred. This method, what is called a type on demand, and Contini Although it is applicable to Yuasu type all, In especially a type on demand, it is a fluid (ink). Electricity arranged corresponding to the sheet and liquid flow channel which are held On a heat conversion object, The rapid rise in heat which corresponds to recorded information and exceeds nucleate boiling is given. At least one drive signal is impressed, an electric heat conversion object -- heat Enel Gee is made to generate -- the thermal action side of a recording head is made to produce film boiling -- consequential -- This Fluid corresponding to a drive signal at 1 to 1 (ink) Effective, since inner air bubbles can be formed it is . passing the opening for discharge by growth of these air bubbles, and contraction -- fluid (ink) it is made to breathe out -- at least one drop is formed. this drive signal is made into pulse shape Fluid (Ink) which was excellent in especially the response since growth' contraction of air bubbles was performed appropriately instancy discharge -- it can attain -- it is desirable.

0165It is considered as the form of the ink-jet recording device using the second dynamic energy. The and nozzle formation board which has a plurality of nozzles, Pressure which counters a nozzle and is arranged Pressure generating element which consists of Electricity material and electric conduction material, the circumference of this pressure generating element is filled it has ink -- a pressure generating element is displaced with impressed electromotive force -- the small droplets of ink -- A Mention A do to the Demand ink-jet record made to breathe out from Jump. It can do.

0166an ink-jet recording device -- above -- a head and an ink tank -- another -- What [ uses a Noodle thing for one impossible / not only the thing used as the body but their separation ] it may be . moreover -- an ink tank receives a head -- that separation is possible or separation -- impossible -- unification -- it is provided in the fixed part of a device besides what is carried in a Have been carriage -- inn Also that of the form which supplies ink to record via a The supply member, for example, a tube, at A do . Composition for making desirable negative pressure act to a recording head When providing in a Ink tank, An absorber is arranged to the Ink stowage of an ink tank. The content volume of opposite Perilla frutescens (L.) Britton var. crispa (Thunb.) Decne. is extended to the form carried out or a flexible ink accommodation bag, and this. A form with the spring part which acts the energizing force of a direction, etc. are employable. Form of the line pudding evening in which a record element is made to come to align over the range corresponding to the full width of the recording medium besides a recorder and the thing which takes a serial recording method as mentioned above Voice may be taken.

(EXAMPLE)

0168Hereinafter, although the present invention is explained still in detail using an example and a comparative example, unless the present invention and its gist are exceeded, it is not limited at all by the following example. in addition -- as long as there is no specification especially -- the ink ingredient of an example and a comparative example -- "mass part" -- means.

0169<Composition of a color material>

0170(1) Copper phthalocyanine tetra sulfonic acid tetra sodium salt (go thing (2)) Composition Compound (2)

0171<img file="WO2006011663A1_D0013.tif" />Sour Holan and 4 -- sulfo phthalic acid monosodium salt, ammonium chloride, urea, ammonium molybdate, and copper chloride (pi) it mixes -- it washed by Me evening A after agitating - Le. then, water is added -- sodium hydroxide solution is used -- the pH of solution was adjusted to 11. Aqueous hydrochloric acid was added to the obtained solution under churning, and also sodium chloride was added gradually, and the crystal was deposited. The obtained crystal was filtered. A thing is washed in 20% sodium chloride solution, then, the crystal which added methanol and deposited is filtered -- it is made to dry after washing in 70% methanol solution -- combination the copper phthalocyanine tetra sulfonic acid tetra sodium salt of thing (2) -- blue crystal Carry out. It was.

0172(2) Copper phthalocyanine tetra sulfonic acid chloride (compound (3)) Synthesis Compound (3)

0173<img file="WO2006011663A1_D0014.tif" />copper phthalocyanine tetra sulfonic acid obtained above in chlorosulfonic acid Tetra sodium salt (compound (2)) it adds gradually -- further -- a thionyl chloride -- drop it gives -- it reacted. then, reaction liquid is cooled -- the precipitated crystal is filtered -- copper Off The Sweat cake of evening Russianin tetra sulfonic acid chloride was obtained.

0174(3) Composition of following compound (4)

0175it sets to compound (4) and general formula (I V) -- Y -- a Amino machine and R₂It is a compound which is the sulfonic group replaced by the 2 or 5th place of But.

0176Compound (4)

0177<img file="WO2006011663A1_D0015.tif" />the inside of ice water -- Ripar OH, cyanuric chloride, and Aniline 1 -- 2 and 5 -- disulfon acid monosodium salt is added -- while adding sodium hydroxide solution -- a reaction -- Went. next, sodium hydroxide solution is added in reaction liquid -- the pH of reaction liquid -- one It adjusted to 0. 28 % ammonia solution and ethylene diamine are added to this reaction liquid -- it reacted. sodium chloride and concentrated hydrochloric acid are dropped at the obtained reaction liquid -- crystal It was made to deposit. carrying out filtration preparative isolation of the precipitated crystal -- 20% sodium chloride solution -- Washing is carried out -- the wet cake was obtained. the obtained wet cake -- methanol and water it adds -- it further filters -- it is made to dry, after washing with methanol -- compound (4) was obtained.

0178(4) Composition of color material A*E

0179inside of ice water, the wet cake of the copper phthalocyanine tetra sulfonic acid chloride (compound (3)) obtained by (2) is added -- you make it agitated and suspended -- further -- Vanmona water, compound (4.) obtained by (3) is added -- it reacted. This Water and sodium chloride were added and the crystal was deposited. the obtained crystal is filtered -- making it wash and dry, after washing in sodium chloride solution and filtering again -- as a blue crystal -- color; *alpha was obtained. the above-mentioned reaction to this compound -- illustration compound 1 -- a table -- it is a To be compound -- the average of the substitution cardinal number in general formula (I) -- 1 = 0.9-1.4 and m=l. -- it is a color material shown in 6*2.1 and n = 2.0*2.5 It is presumed.

0180it is a compound denoted by the same synthetic flow as the above with illustration compound 1 -- the average of the number of substitution go in general formula (I) compounded color material B*E different, respectively. the average of the substitution cardinal number in color material A*E -- the following table -- it is shown in 5. Table 5

0181Color material 1 m n

0182A 0.9~1.4 1.6--2.1 2.0--2.5

B 0 1.5--2.0 2.0--2.5

O 0 1.4--2.4 1.6--2.6

D 0 1.5--2.5 1.5--2.5

0186E 0 2.5--3.0 0.5--1.0 Evaluation > of bronze-proof [ < ] nature

0187(1) Manufacture of ink

0188the following table -- 6 and a table -- after mixing each ingredient shown in 7 and agitating enough, it filters under pressure in the membrane philharmonic evening 1 of Pore size 0 .2 m -- ink 1*1 Prepare 7. It was.

0189Table 6

0190<img file="WO2006011663A1_D0016.tif" />

0191(*) Acetylene glycol ethylene oxide addition

0192(Surface activation abatement; product made from Kawaken fine Chemical)

0193Table 7

0194<img file="WO2006011663A1_D0017.tif" />

0195(*> acetylene glycol ethylene oxide addition)

0196(Surface-active agent; product made from river 5* fine chemicals) (2) d₇₅Measurement of a value.

0197About ink 1*17, it is a baby square. A scattering angle profile is measured by the X-rays scattering-about method. It carried out. using pure water in measuring -- color material concentration -- all the ink mass -- an opposite -- it diluted so that it might carry out and might become 0. 5 mass % -- Dilution, Inc. was used. Scattering angle profile The measurement conditions of an isle are as being shown below.

0198* Device: Nano V i ewe r (product made from physical science)

0199* X line source: Cu -- kappaalpha

0200* Output: 45 kV - 60 mA

0201* Effective focal spot: 0. 3 mm phi+Con f o c a l Max -- F l ux M i r r o r

0202* 1^{s t}S 1 i t : 0.5 mm, 2^ndS 1 i t : 0. 4 mm, 3^rdS I i t : 0. 8mm

0203* Irradiation time: 240 m i n

0204* Beam stopper: 3. omicronpiiotapiiota

0205- Measuring method : penetration method

0206* Detector : B l ue Imag i n P l a t e

0207Obtained Scatter X diffraction data-processing soft J ADE (M a t e r i a lDa t a, I n c.) from an angle profile is used, ; 20 values in which a It was peak area and 75% or more of the whole peak area are contained ^ A box round is removed. (20)₇₅Value was measured. 20₇₅It is based on following formula [ from a value ] (2), and is d.₇₅It is Calculation about a value. It took out. a result -- a table -- it is shown in 8. rf₇₅= -- Formula (2)

02082 Sin Theta₁₅

0209(4) Measurement of maximal absorption wavelength (Amax)

0210After diluting ink 1*17 with pure water 2000 times, respectively, it is a maximal absorption wave. Merit was measured. a result -- a table -- it is shown in 8. the measurement conditions of maximal absorption wavelength (Amax) -- with -- It is as being shown below.

0211* spectrum photometer: -- the account of self--- a spectrum -- photometer (brand name: U -- 3300; Hitachi make) * measurement cell: 1-cm quartz cell

0212* Sampling interval: 0. 1 nm

0213- Scanning speed: 30 nmZm i n

0214* Measurement count: 5 times measurement average

0215(4) Creation of a recorded matter

0216To ink-jet recording device (brand name: product made from P i xu s .950 i; canon) Ink 1*17 obtained above is carried, respectively, gloss Mede for ink-jets The (brand name: product made from PR 101; canon) Into printing du t y -- 5, 12, 21, 29, 35, 43, 51, 58, 66, 74, 85, 90, and 100% -- change -- the gradation pattern of 13 steps of Did is printed -- the recorded matter was created.

0217(5) Criticism of bronze-proof nature

0218it sets to 13 steps of gradation patterns of the recorded matter obtained above -- bronze phenomenon occurring printing d u t y is checked visually -- the printing d u t y -- a bronze phenomenon -- Depart It was considered as printing du t y which carries out raw. Generally printing d u t y of a bronze phenomenon becomes high. It follows and there is a tendency which is [ become ] easy to generate. That is, seal which a bronze phenomenon generates that it is easy to generate a bronze phenomenon, so that printing du t y which . bronze phenomenon generates is low It can be said to be the ink which a bronze phenomenon does not generate easily, so that character du t y is high. Bron-proof The standard of A nature is as follows. an evaluation result -- a table -- it is shown in 8.

0219A A : printing du t y which a bronze phenomenon generates is 85% or more.

0220A: Printing d u t y which a bronze phenomenon generates is 66% or more and less than 85%. B: Printing d u t y which a bronze phenomenon generates is 43% or more and less than 66%. C: Printing d u t y which a bronze phenomenon generates is more than 29 % and less than 43 %. D: Printing d u t y which a bronze phenomenon generates is less than 29 %. Table 8

0221<img file="WO2006011663A1_D0018.tif" />

0222This application is 2. July 2, 004 Japan patent application No. 20 for which it applied on the 9th 0 4 - 2 2 1 8 3 1 and 200 The Japan patent application watch for which it applied on July 26, 5 Issue 200 5 - 2 1 6 22 The right of priority from 9 is claimed. it is -- among those, Capacity It quotes and makes it a part of this application.