CN1162930A - Process for preparing a dispersion of hard particles in solvent - Google Patents

Abstract

A process and a high pressure apparatus are disclosed which are useful in preparing magnetic dispersions and other dispersions of hard, non-compliant particulates. The apparatus can be monitored for clogs and wear and allows for relatively quick and inexpensive replacement of orifices. The apparatus includes a high pressure pump and a series of impingement chambers comprising an input manifold where the process stream is split into two or more streams and an output manifold where the streams are recombined after passing through restrictive orifices configured in such a manner that the streams impinge on each other at high velocities. The orifices in each succeeding impingement zone are the same size or smaller than the orifices in the preceding impingement zone, and the orifices in the final impingement zone must be smaller than the orifices in the first impingement zone.

Description

The manufacture method of dispersion of hard particles in solvent

Technical field

The present invention relates to hard, inflexibility (non-compliant) and the manufacture method and the equipment of the solvent dispersion of indeformable particle basically.The present invention be more particularly directed to the manufacture method of magnetic paint dispersion.

The background of invention

The dispersion of hard inflexibility particle can be used for different technical fields, comprises the field of grinding coating, printing ink, paint and anti-decolouring (Color proofing) and so on.A kind of to use the field of the dispersion of hard inflexibility particle be magnetic recording medium, as audio tape, video-tape, data storage belt or computer disk.In making this magnetic recording medium process, the magnetic paint particle and the polymer adhesive that generally will be dispersed in a kind of solvent are coated in a kind of substrate.Drying stays one deck magnetic pipe recording material layer after removing and desolvating.

The mixing technology working medium of processing magnetic paint dispersion grinds at present, as ball milling, sand milling or attritor.By mixture being carried out the little shearing of high strength, the magnetic paint dispersion that medium mill can obtain to be suitable for because the little shearing of high strength broken basically the granule of granules of pigments.Yet these medium mill systems of processing have some defectives, comprise that the medium wearer pollutes, as the sand grains in the dispersion.In addition, the process velocity of medium mill is limited.If the circulating rate in the increase medium mill will produce uneven grinding and dispersion, many materials were not fully handled the system of just having left.So need overcome these defectives in the medium mill process technology with the high-pressure system of homogenizer and emulsifier and so on.

The effect of homogenizer and emulsifier generally is to force the pre-composition of solid and liquid and a surface or mutual bump.Unfortunately, the dispersion of processing rigid inflexibility particle is difficult in the high-pressure emulsification device, and this is that these crumb structure may be stopped up the slit that mixture passes through because the abrasiveness and the crumb structure size of particle are bigger.In order to overcome this blockage problem, United States Patent (USP) 4,533,254 and 4,908,154 require to filter or preliminary treatment before using high-pressure homogenizer or emulsifier, with granularity that reduces pigment and the fine dispersion of guaranteeing pigment.

In addition, the abrasiveness of magnetic paint can rapid wearing bump chamber.The wearing and tearing of restive existing homogenizer or emulsifier and obstruction and can not cheap and promptly change the major obstacle that the parts that worn and torn are to use high-pressure installation.

At last, the operating pressure of existing homogenizer or emulsifier generally is no more than 30000 pounds/inch ²(205MPa), the result has limited the operating energy that can apply mixture.But please note that Japanese publication 05098192 and JP0509188 point out that spraying the preferable range of clashing into pressure is 1400-140000psi (9.8-980Mpa).These two applications are Dainippon Ink﹠amp; Chemical company, and disclosed how to obtain the polymer latex liquid suspension.

Prior art has also disclosed when making the magnetic paint dispersion and has used preprocess method before the medium milling more fortunately.This preliminary treatment is adding whole magnetic paints, partial solvent and randomly partly or entirely carrying out behind polymer adhesive and other additive at least usually.By promoting surfactant, polymer etc. preliminary wetting and from the particle surface replaces air to pigment, preliminary treatment has improved later operation and processing (grind etc.).Super mixer, homogenizer, kneading machine and planetary-type mixer have been used for this method.

The general introduction of invention

The inventor has invented a kind of improved injection impact system of making the good dispersion of hard inflexibility particle.The present invention is a kind of high-tension apparatus that can be used for making hard inflexibility particle dispersion.This equipment comprises high-pressure pump and the series of being made up of two bump chambers at least.The bump chamber comprises inlet manifold and the outlet manifold by behind the throttle orifice (restrictive orifices) these liquid streams being mixed again that working solution stream is divided into two or more liquid streams.The structure of bump chamber can make liquid flow mutual high-speed impact.The size of throttle orifice is identical with throttle orifice in the previous impingement region or less than the throttle orifice in the previous impingement region in the impingement region in back.And the throttle orifice in last impingement region must be less than the throttle orifice in first impingement region.The inventor finds can obtain good dispersion, and blockage problem can be reduced to a minimum with the orifice dimensions that diminishes gradually.In addition, the inventor has found at least one bump chamber the distance (Di) between throttle orifice outlet and rum point to be remained on the quality that the twice that is no more than the throttle orifice diameter can improve dispersion.

The throttle orifice device is better installed like this, so that this throttle orifice device can be vibrated.The wearing and tearing much less that this throttle orifice device that freely carries is subjected to than fixed orifice that can not free vibration.Particularly, when the arrival end of throttle orifice device was fixed, the port of export of throttle orifice device preferably can free vibration.

This device can be monitored and be stopped up and wearing and tearing (for example using the pressure monitoring meter).In addition, this device can be faster and is changed throttle orifice at an easy rate.This system can be used for making the dispersion of the dispersion of hard particles, particularly magnetic paint.

In addition, the present invention is a kind of manufacture method that contains the dispersion of solvent and hard inflexibility particle, and this method comprises the steps:

A) dispersion components is mixed into the diffusing mixture of half point;

B) to this mixture pressurization; And

C) make pressurised mixt pass through a series of being made up of two bump chamber devices at least, wherein each bump chamber device is divided at least two liquid streams with mixture, make each liquid stream by the throttle orifice device, and liquid flows bump mutually when leaving the throttle orifice device.The diameter of each throttle orifice reduces step by step, and the distance (D of throttle orifice outlet and rum point _i) be no more than throttle orifice diameter (d _o) twice.

Dispersion better contains the hard inflexibility particle up to 60% volume.

According to another embodiment, the throttle orifice that pigment dispersion is reduced by a series of diameters, rather than logistics shunted and collaborate.The throttle orifice that a series of diameters reduce is meant that the diameter of back throttle orifice is not more than the diameter of front throttle orifice, and last throttle orifice is less than first throttle orifice.Yet each diameter can have more than one throttle orifice.

Brief description of drawings

Fig. 1 is the schematic diagram of entire equipment of the present invention, and it comprises high-pressure pump and impingement region series.

Fig. 2 is the schematic diagram of used each of equipment bump chamber device among Fig. 1.

Fig. 3-the 5th, the viewgraph of cross-section of throttle orifice device version.

Fig. 6 is the viewgraph of cross-section of another inlet manifold.

The detailed description of invention

The present invention need not the dispersion that preliminary treatment in the medium mill or pre-filtering just can be made hard inflexibility particle. Hard inflexibility particle refers to basically indeformable particle. The example of hard inflexibility particle includes, but are not limited to magnetic paint, such as iron oxide, barium ferrite, metallic particles and chromium dioxide; Carbon black; Many coloring pigments are such as the phthalocyanine of CuPc and so on, aniline black byestuffs, the blue dyestuff of aniline, chrome yellow, Du Pont's oil red (E.I.Du Pont Company's manufacturings), Monoline is yellow, Sunfast is blue, Sun is yellow, Sun is red and other pigment available from Sun chemical company, Harmon Quindo are red, Regal300, Fluorol Huang 088, yellow S0790, the Ultramarine orchid of Fluorol Green Gold 084, Lumogen, Ultramarine are purple, ferric ferrocyanide and other pigment available from BASF, Malachite Green Oxalate, dim, rose-red and Malastral is red; Titanium dioxide; Grinding-material is such as aluminium oxide, carborundum, alumina, cerium oxide, zirconia, silica, boron carbide and garnet etc.

Referring to Fig. 1, this method comprise with hard inflexibility particle (better being the magnetic paint particle), solvent and optionally other material join in the container 20, with any thick mixed cell 21 of high speed dissolver type blender and so on it is mixed into half premix that disperses. Shar, Inc.D-5C blender and Cowels blender are two kinds of very applicable blender examples. Do not need further preliminary treatment (medium mill or filtration) to prevent that the high-pressure injection impact system from being stopped up by the granule of particle. Still can process up to 60 purpose granules. Workable mixtures better contains the solid up to about 85% weight, for magnetic paint, better contains the solid of 20-50 weight. Take volume as benchmark, the content of solid can be up to 60 volume %. For the magnetic paint dispersion, volume % is preferably 10-20 volume %. The largest particles content of available injection impact system processing depends in part on the type of processing granular. For example, it is high that the content of the comparable aciculiform magnetic paint of Spherical alumina particles is wanted, such as 80% weight or 50% volume. If also use another kind of solid constituent (such as polymer adhesive) except hard inflexibility particle, then the maximum level of hard inflexibility particle may reduce. When making the magnetic paint dispersion with polymer adhesive, the % volume of solid can be 5-18%.

Before spraying bump, use double planetary mixer be one preferred embodiment. Use the double-planet blender can produce more stable dispersion, the injection bump that this dispersion is conducive to is subsequently processed. When carrying out this step, dispersion does not generally contain all components of final dispersion. For example, can only carry out this step to pigment and partial solvent, maybe can comprise all or some other dispersion components. Solids content used in the double-planet blender is higher, therefore may need dispersion is diluted before spraying bump. For example, can process the magnetic paint of 55-85% weight or 12-40% volume solid in the double-planet blender. Different magnetic paints is better processed by the different piece of this scope. For example, metallic pigments are better processed by the low side of this scope, and iron oxide is better processed by the intermediate value of this scope, and barium ferrite is better processed by the high-end of this scope. Because higher solids content after double-planet mixes needs this dispersion is diluted to suitable percentage by volume or percetage by weight before further processing.

Then premix is transported to high-pressure pump 23, better by low-lift pump 23, this pump can produce the liquid discharge pressure of about 50-150 psi (300-1000kPa). More handy high-pressure pump 23 is elevated to the pressure of working solution stream more than the 30000psi (205MPa). Have now found that the enhancing pump performance is good. For this system can effectively be worked, all dispose wear-resisting check valve 24 in the front and back of high-pressure pump, to prevent the backflow of working solution stream. The reliability that strengthens pump depends on that check valve can both work in whole pressure and stroke speed scope. During the processing grinding material, the wearing and tearing of the valve that is caused by the pressure that increases and flow velocity, throttle orifice etc. have limited operating pressure and flow velocity that existing system can use. The commercially available one-way valve designs that inventor's discovery is installed in existing production scale system of processing be not suitable for the grinding-material dispersion up to the pressure of 60000psi with above under the flow conditions of 0.25 gpm. Suitable check valve is disclosed in the uncensored U.S. Patent application 08/339,027.

Then pressurized operation liquid flows to into impingement region series 1. The minimal amount of independent injection bump chamber device 1a etc. is 2, and the independent injection bump chamber device more than 4 is better arranged, and preferably has 6-9 independent injection bump chamber device. For the magnetic paint dispersion, should be at least 30000psi (205 Mpa) by the pressure drop of clashing into chamber series, surpass better 35000psi (240MPa), surpass best 40000psi (275MPa). One preferred embodiment in, in the end the pressure drop of bump on the chamber be maximum. If necessary or need, can flow 30 through liquid processes dispersion or the circulation of part dispersion for next round.

Referring to Fig. 2, spray separately the bump chamber device comprise with process streams be divided into two or more independent liquid streams inlet manifold 2, contain the outlet manifold 6 of the bump chamber of again mixing independent liquid stream and with the pipe 3 of independent liquid conductance to the bump chamber. Fig. 2 represents to spray a preferred structure of bump chamber device, in this device working solution stream is divided into two independent liquid and flows. With clamp nut 4 and 5 inlet manifold 2 and outlet manifold 6 are connected on the high-voltage tube 3. Outlet manifold 6 itself preferably can be dismantled, if parameter that like this need to be different or these parts are worn or stop up, with regard to replaceable throttle orifice cone 8 and extension 9. High-voltage tube 3 optionally assembles thermocouple and pressure-responsive device, so that the operator of system can detect the flow abnormalities of obstruction and so on. Impinging upon in the bump path 10 of working solution stream carried out.

Each liquid is flow to another liquid of few guiding stream in that bump is indoor, and liquid stream is reconsolidated. In other words, as with two liquid stream, two outlets must be in identical plane, but mutual angle can be different. For example, the angle between two liquid flow can be for 60,90,120 or 180 degree, although any angle all can be used. If use four liquid streams, wherein two can merge at the top of bump chamber, and two can merge at the middle part of bump chamber 10 in addition, and perhaps four liquid streams all merge at the top of bump chamber. Although the throttle orifice cone is better mutually vertical with the bump passage with extension, this is unnecessary.

The various embodiments of bump throttle orifice device 7 are sprayed in Fig. 3 to 5 expression. Referring to Fig. 3 to 5, throttle orifice cone 8 can be the parts that separate with extension 9, but generally is combined into parts. Throttle orifice 31 is fixed in the throttle orifice cone 8. Throttle orifice is made with the durable material of hard. Suitable material is sapphire, tungsten carbide, stainless steel, diamond, ceramic material, carbide alloy and hardening metal composition. Throttle orifice can be ellipse, hexagon, square etc. Yet the throttle orifice that is roughly circle is made easily and is subject to wearing and tearing more uniformly. As previously mentioned, the outlet of throttle orifice device needs energy free vibration. For example, for the tungsten carbide throttle orifice in the stainless steel sleeve pipe, the distance of dispersion discharge point should be at least with rum point distance (Di) 13 times in the rigid type bearing of throttle orifice device and the throttle orifice.

The mean inside diameter of throttle orifice partly depends on the size of processed individual particle. During preparation magnetic paint dispersion, preferred throttle orifice diameter is 0.005-0.05 inch (0.1-1 millimeter). Preferably the internal diameter of throttle orifice is equal to or less than the internal diameter that throttle orifice in the chamber is clashed in the front in all bump chambers, back. If need to keep in a long time higher working solution flow rate, then can increase the length of throttle orifice. Liquid flowing rate during by throttle orifice is generally greater than 1000 feet per seconds (300 meter per second).

Extension 9 remains to injection stream speed near independent liquid and flows mutual rum point part.The internal material of extension can be identical or different with the material of throttle orifice, and its diameter can be identical with the diameter of throttle orifice or slightly different.The length of extension and extension export to the decentralization that the distance of clashing into the center, chamber can influence gained.For the magnetic paint dispersion, the distance that extension exports to the impingement region center should be no more than 0.3 inch (7.6 millimeters), better is no more than 0.1 inch (2.54 millimeters), preferably is no more than 0.025 inch (0.6 millimeter).

The inventor finds, is unnecessary though provide filter at the upper reaches of first bump chamber device, may be useful.The purpose of this filter mainly is to remove bigger (as greater than 100 microns) pollutant, and does not remove granules of pigments.In addition, the inventor has developed the improved inlet manifold 2 ' shown in a kind of Fig. 6, and this manifold comprises a filter.This inlet manifold 2 ' comprises a dismountable cladding system 26, and this device can be used for dismantling and changing the filter cell 29 that is contained in the shell 28.Potted component 27 prevents to leak out work materials from inlet manifold.

In addition, the inventor finds to use this injection impact system can allow dispersion after the processing by the resistive filter that transfinites (ultrarestrictive filter).In the present invention, the resistive filter that transfinites is the filter that can remove 0.8 micron particles with 99% efficient.Filter used in this method better can be removed about 99% 0.6 micron particles, better can remove about 99% 0.5 micron particles.Because the reduction of viscosity and the particle granule that reached in the injection bump part of this method is cracked, this super restrictive filter can be used for the dispersion of solids content higher (20-50%), and need not often to change filter.

The example of the suitable commercially available resistive filter that transfinites comprises Nippon Roki HT-04, HT-05, HT-06 and HT08.May need to use a series of these filters.Have now found that the resistive filter that progressively increases of four limits of serial connection can obtain good result.

The inventive method and equipment can be used for making the dispersion of most solid in liquid.Yet be specially adapted to make the dispersion of hard inflexibility particle.If change of granularity, the size that then needs to regulate throttle orifice and extension.The magnetic paint dispersion generally comprises various other additives of magnetic paint particle, solvent, polymer adhesive and lubricant and so on.

According to another embodiment of the invention, replace the series of impingement region or chamber 1 with a series of throttle orifice devices.These throttle orifice devices are identical with shown in Fig. 3 to 5 better.These a series of throttle orifice devices are characterised in that the throttle orifice internal diameter of all back is equal to or less than the internal diameter of last throttle orifice, and last throttle orifice diameter is less than the diameter of first throttle orifice.The throttle orifice that these a series of diameters successively decrease produces good dispersion by using high tensile force, and described high tensile force is to produce owing to making dispersion pass through little throttle orifice.Reduce the diameter of each follow-up throttle orifice in this series, can obtain better dispersion, and the increase that can not produce excessive obstruction, pressure or temperature.

Except with this method and equipment as prepare the method for magnetic dispersion, the inventor also finds to use a series of high-pressure injections to clash into chamber devices can provide good preliminary treatment.Handle with medium mill or the injection bump that carries out other routinely then and prepare magnetic dispersion.

Embodiment

Embodiment 1

Cobalt improved γ-the Fe that will contain 47% weight ₂O ₃, the solid-state dispersed lubricant (Emcol andPOCA) of 1.5% weight, the carbon black of 2.5% weight and the slurry of 49% oxolane be placed on Shar, carries out premix among the Inc.D-5C.Then this mixture is pumped into the enhancing pump, be forced into 25000-45000psi.The mixture that makes pressurization is by four injection percussion device series, and each throttle orifice internal diameter that sprays percussion device is all less than the injection percussion device of front.The throttle orifice internal diameter is respectively 0.030 inch (0.76 millimeter), 0.026 inch (0.66 millimeter), 0.022 inch (0.56 millimeter) and 0.018 inch (0.46 millimeter).Flow speed stability is at 1.268 gpms (4.8 liters/minute).Carry out five circulations; Being about to slurry handles in system five times.Export to four batches of products of different distance (hereinafter referred to as " free distance ") manufacturing of the center line of bump passage respectively with extension.Measure the outlet temperature (measuring) of 45 degree gloss, inlet pressure (recording) and the slurry of each circulation at the upper reaches that is right after first bump chamber device with being placed on the high pressure thermojunction that is right after last impingement region back.

The results are shown among the table 1-3.45 degree gloss measurements show when free distance reduces that the quality of dispersion will improve.Outlet temperature and inlet pressure when outlet temperature when simultaneously free distance is 0.025 inch (0.635 millimeter) and inlet pressure are significantly higher than the bigger free distance of use.There is not tangible pressure reduction when using 0.1 inch (2.54 millimeters), 0.3 inch (7.62 millimeters) and 0.4 inch (10.2 millimeters) free distance.

Table 1

To the influence 45 ° gloss of rum point free distance to the ferromagnetism dispersion

	The bump distance
					Process cycles	" 0.4 (10.2 millimeters)	" 0.3 (7.62 millimeters)	" 0.1 (2.54 millimeters)	" 0.025 (0.635 millimeter)
The 1st time	????26.8	????34.6	?????41.5	?????42.5
					The 2nd time	????34.0	????47.7	?????51.5	?????54.5
The 3rd time	????47.5	????51.8	?????56.0	?????59.0
					The 4th	????50.7	????50.4	?????59.5	?????62.8
The 5th	????53.6	????53.4	?????61.0	?????64.8

Table 2

To the influence Mpa of rum point free distance to ferromagnetism dispersion/inlet pressure response

	The bump distance
					Process cycles	" 0.4 (10.2 millimeters)	" 0.3 (7.62 millimeters)	" 0.1 (2.54 millimeters)	" 0.025 (0.635 millimeter)
The 1st time	?????216	?????226	?????198	??????258
					The 2nd time	?????192	?????182	?????193	??????266
The 3rd time	?????205	?????189	?????189	??????261
					The 4th	?????212	?????187	?????180	??????273
The 5th	?????219	?????217	?????183	??????286

Table 3

To the rum point free distance to the influence of ferromagnetism dispersion/inlet temperature response ℃

	The bump distance
					Process cycles	" 0.4 (10.2 millimeters)	" 0.3 (7.62 millimeters)	" 0.1 (2.54 millimeters)	" 0.025 (0.635 millimeter)
The 1st time	????38	????49	????89	?????108
					The 2nd time	????37	????39	????86	?????106
The 3rd time	????39	????37	????94	?????111
					The 4th	????41	????36	????97	?????121
The 5th	????43	????38	????97	?????123

Embodiment 2

4 injection percussion devices processing with serial connection contain the cobalt improved γ-Fe of 41.2% weight ₂O ₃, 2.8% solid-state dispersed lubricant, the MEK of 43.4% weight and the slurry of 12.6% cyclohexanone.Each sprays the throttle orifice internal diameter of percussion device less than previous injection percussion device.The throttle orifice internal diameter is respectively 0.030 inch (0.76 millimeter), 0.026 inch (0.66 millimeter), 0.022 inch (0.56 millimeter) and 0.018 inch (0.46 millimeter).Flow speed stability is at 1.268 gpms (4.8 liters/minute).Carry out five circulations; Being about to slurry handles in system five times.The structure of the throttle orifice device of preceding 3 impingement regions as shown in Figure 3.The internal diameter of extension is 0.025 inch (0.635 millimeter) in preceding 3 bump chambers.In first, in the 4th percussion device the structure of throttle orifice device as shown in Figure 3, its throttle orifice length is 0.030 inch (0.76 millimeter).In second batch, the structure of throttle orifice device as shown in Figure 4, having length is the extension discharge orifice of 0.250 inch (6.3 millimeters).

The results are shown among the table 4-6.Have higher gloss response by the dispersion that has in the percussion device in the end than the system of meropodium discharge orifice length, show and disperse better.In addition, also increased by temperature and pressure response than the dispersion of growing restricted throttle orifice.

Table 4

Throttle orifice length is to the 45 ° of gloss that influence of ferromagnetic dispersion

	The length of throttle orifice
			Process cycles	" 0.03 (0.76 millimeter)	" 0.250 (6.3 millimeters)
The 1st time	???????58.3	???????62.2
			The 2nd time	???????56.0	???????65.4
The 3rd time	???????60.5	???????64.5
			The 4th	???????61.5	???????69.4
The 5th	???????61.3	???????70.1

Table 5

Throttle orifice length is to the Mpa that influences of ferromagnetic dispersion/inlet pressure response

	The length of throttle orifice
			Process cycles	" 0.03 (0.76 millimeter)	" 0.250 (6.3 millimeters)
The 1st time	????????252	?????????267
			The 2nd time	????????214	?????????236
The 3rd time	????????201	?????????228
			The 4th	????????193	?????????222
The 5th	????????208	?????????201

Table 6

Throttle orifice length is to the influence of ferromagnetic dispersion/temperature-responsive ℃

	The length of throttling
			Process cycles	" 0.03 (0.76 millimeter)	" 0.250 (6.3 millimeters)
The 1st time	????109	????121
			The 2nd time	????106	????108
The 3rd time	????101	????110
			The 4th	????98	????108
The 5th	????95	????101

Embodiment 3

Handle the MEK, 10.8% toluene, 11.8% cyclohexanone, the 2.2% solid-state dispersant, 30.7% that contain 29.9% weight with 4 injection percussion devices of serial connection and mix cobalt γ-Fe ₂O ₃, 9.4% polyurethane binder solution (solids content is 30% weight in the MEK), 3.0% ethenyl adhesive solution (solids content is 32% weight in the MEK) and 5% head cleaner (is benchmark with metallic pigments weight) the ferromagnetic pigments slurry.Preceding two injection bump chambers have throttle orifice device as shown in Figure 3.The throttle orifice diameter is 0.030 inch and 0.022 inch (0.76 and 0.56 millimeter) in it.Latter two sprays the bump chamber and has throttle orifice device shown in Figure 4, and the sapphire pipe internal diameter of its lengthening is 0.018 inch (0.46 millimeter).Regulate flow velocity, keep all types of target pressure.Keep 18000,24000,30000 and the force value of 36000psi (123,164,205 and 246MPa) respectively in first import department of spraying percussion device, prepare four batches of products.The response of 45 ° of gloss increases with the increase of operating pressure, and this quality that shows dispersion improves with the increase of operating pressure.

Embodiment 4

At Shar, premixed CrO in the Inc.D-5C blender ₂, ethenyl adhesive, polyurethane binder and MEK/toluene/cyclohexanone solvent mixture composition.Then this premix is forced into about 15000psi (103MPa).Make this mixture by different throttle orifice systems.It is that 0.010 inch (0.25 millimeter) and length are four throttle orifices of 0.030 inch (0.76 millimeter) that system A has internal diameter.It is the throttle orifice that 0.030 inch (0.76 millimeter) and diameter are respectively four polyphones of 0.022 inch (0.56 millimeter), 0.018 inch (0.46 millimeter), 0.014 inch (0.36 millimeter) and 0.010 inch (0.25 millimeter) that system B has length.The dispersion quality (representing with filterability) that the system B that successively decreases with the throttle orifice diameter handles is more much higher than the dispersion quality of handling with the identical system A of throttle orifice diameter.The pressure that records when filtering the dispersion of being handled by the A of system is 20-33psi, and required pressure only is about 7-11psi when filtering the dispersion of handling with the B of system.

Embodiment 5

Mix cobalt γ-Fe by one of following method to containing 82.8 weight portion MEKs, 29.6 parts by weight of toluene, 32.2 weight portion cyclohexanone, the solid-state dispersant of 6.0 weight portions and 100 weight portions ₂O ₃Ferromagnetic pigments slurry carry out preliminary treatment.

Sample HS: mixed 5 hours in Ross Verasmixer blender high speed.It is that disc type disperser and the rotating speed of 2500rpm is the uniform mixer of 2945rpm that described blender has the anchor formula blade that rotating speed is 80rpm (diameter of propeller blade is 6 inches (15.2 centimetres)), rotating speed.

Sample DP/HS: solids content be 71.0% o'clock be to mix 3 hours in the double planetary mixer of 115 feet per minutes (35 meters/minute) at tip speed.Be 42.3% with solvent dilution to solids content then, mixed 2 hours in Ross Versamixer blender high speed at last.It is that disc type disperser and the rotating speed of 2500rpm is the uniform mixer of 2945rpm that described blender has the anchor formula blade that rotating speed is 80rpm (diameter of propeller blade is 6 inches (15.2 centimetres)), rotating speed.

Sample HS/JI: mixed 5 hours in Ross Versamixer blender high speed.It is that disc type disperser and the rotating speed of 2500rpm is the uniform mixer of 2945rpm that described blender has the anchor formula blade that rotating speed is 80rpm (diameter of propeller blade is 6 inches (15.2 centimetres)), rotating speed.Circulated 3 hours in a series of injection rams then, the flow velocity in the ram is about 1.2 gpms (4.5 liters/minute), and pressure is about 41000psi (282MPa).The throttle orifice internal diameter is that six and throttle orifice internal diameter are arranged is that 0.046 centimetre impingement region has 4 to 0.076 centimetre, 0.056 centimetre impingement region.

Under the 10000r/s condition, measure the shear viscosity (is unit with the centipoise) of these dispersions with the ICI viscosimeter.Also with these dispersion manual application on pet film, and in addition dry.Measure glossiness, the factor of quality (Goodness) value (GN of manual application thing (handspreads), coercivity is divided by the zero dimension coercivity value that coercivity produced of half-peak eminence), remanent magnetism (Br, with the corresponding maximum residual flux density of saturation flux density value), squareness ratio (Squareness) (Sq., referring to United States Patent (USP) 5,081,213, the 11 hurdles) and Roden Stock (RS).The results are shown in the following table:

Sample	Viscosity	???GN	Glossiness	?????Br	????Sq	????RS
							??HS	???10	??2.13	????22	????1226	????0.77	????25
?DP/HS	???19	??2.20	????35	????1409	????0.79	????19
							?HS/JI	????7	??2.45	????60	????1610	????0.83	????7.5

Have than the better viscosity of other sample, factor of quality value, glossiness, remanent magnetism, squareness ratio and RS with spraying the pretreated dispersion of ram.

Embodiment 6

Mix cobalt γ-Fe with the high shear mixing method in the Ross Versamixer blender or with the mixed method in the duplicate rows star blender to containing 82.8 weight portion MEKs, 29.6 parts by weight of toluene, 32.2 weight portion cyclohexanone, the solid-state dispersant of 6.0 weight portions and 100 weight portions ₂O ₃Ferromagnetic pigments slurry carry out preliminary treatment.The solvent that in the preliminary treatment mixture, adds ethenyl adhesive (9.2% weight is benchmark with the oxide weight) and polyurethane binder (about 12% weight is benchmark with the oxide weight) and replenish.The percentage by volume of last solid is lower than 20%.With sand mill or high-pressure injection impact system whole mixtures are handled then.Sample is as follows:

Sample	Pre-blend approach	Process for dispersing
			????6A	????Versamixer	Sand milling
????6B	????Versamixer	Spray bump
			????6C	Double planetary mixer	Sand milling
????6D	Double planetary mixer	Spray bump

Make the hardened coating thing of various dispersions, and measure its coercivity (Hc), remanent magnetism (Br), factor of quality hardened coating thing value (GN, coercivity is measured divided by the coercivity zero dimension of the coercivity width gained of half-peak eminence), squareness ratio (Sq.) and Roden Stock (RS).Equally also measure the viscosity of dispersion.The results are shown in the following table:

Table 7

Sample	??Hc	???Br	????GN	???Sq	Glossiness	????RS	Viscosity
								??6A	??775	??1315	???1.93	??0.764	???41	????10.7	????40
??6B	??764	??1413	???2.16	??0.798	???50	????9.6	????17
								??6C	??768	??1340	???2.01	??0.787	???47	????9.9	????45
??6D	??751	??1277	???2.14	??0.797	???45	????10.9	????26

Grain size analysis

The grain size analysis of dispersion is an index that reduces in the process.According to the particle size range of institute's analysing particulates, use two kinds of methods, i.e. Microtrac ^TMAnd photon correlation spectroscopy (PCS).When being the 0.2-700 micron, particle size range uses Microtrac ^TMMethod.To cycle through Microtrac to used similar solvent in the sample ^TM(available from Leeds and Northrup, St.Petersburg FL), drips sample to X100 then, till concentration is enough to make this instrument to carry out grain size analysis.Laser by the sample after diluting, is measured forward scatter.The result of output is number average particle size (Mn), the equal granularity of body (Mv) and volume particle size distribution.When granularity is used PCS during less than 3 microns.With similar solvent with sample be diluted to be placed on Malvern photon correlation energy spectrometer 4700 (available from Malvern Instruments, Inc., Southboro is enough to record the concentration (generally being about 0.01% volume) of a per second 60000-120000 reading in MA).Allow the sample of laser by diluting, light be done the granule proliferation scattering of cloth youth motion, its intensity is recorded as average viscosity or is similar to Microtrac ^TMThe Zave of Mn.

Embodiment 7

Prepare graining paste with the following method, promptly earlier at 252.0 parts of 2-butanone (available from Ashland Chemical Co., Columbus, a kind of solvent of OH) and 168.0 parts of GLYCOL ETHER PM ^TMAdd 14.5 parts of BUTVAR in (available from a kind of solvent of AshlandChemical Co.) ^TMB-98 (available from Monsanto Company, St.Louis, a kind of resin of MO), 14.5 parts of JONCRYL ^TM67 (available from S.C.Johnson﹠amp; Son, Inc.Racine, a kind of resin of WI), 7.3 parts of DISPERBYK ^TML61 (available from BYK Chemie, Wallingford, a kind of dispersant of CT, the concentration in the n-butyl acetate is 30%) and 0.15 part of FLUORAD ^TMFC-430 (available from 3M Company, St.Paul, a kind of coating additive of MN); Stirred 30 minutes with air mixer, till resin dissolves.Add 43.6 parts of SUNFASTBLUE then ^TM248-0615 (available from Sun Chemical Corp., Cincinnati, a kind of pigment of OH), and be stirred to slurry evenly till.This slurry is placed in the loading hopper, is forced into 97-110MPa (14000-16000psi) with air driven pump, make its injection percussion device that passes through three polyphones, each sprays the throttle orifice internal diameter of the throttle orifice internal diameter of percussion device less than previous injection percussion device.The throttle orifice internal diameter is respectively 0.46 millimeter (0.018 inch), 0.30 millimeter (0.012 inch) and 0.23 millimeter (0.009 inch).Flow velocity maintains 400 ml/min.Slurry is cycled through this percussion device series, turn back to loading hopper then, carry out 42.9 circulations altogether.Take out 2 milliliters of samples since 2.9 circulations by different intervals.Percussion device is immersed in the mixture of ice and water, making slurry temperature (with the thermometer measure that is placed in the loading hopper) is 36 ℃ at the 7th circulation time, is 40 ℃ at 34 circulation times.Use Microtrac ^TMMeasure the granularity of each sample with PCS.Take out from loading hopper in back 4 hours, each sample is with the coating of No. 6 Meyer rods, and the thickness of wet coating is 14 microns, is placed in 93 ℃ of air circulation ovens dry 2 minutes, the measurement transparency.When anti-decolouring, the covering order of color requires minimum transparence value, makes a kind of opacity of pigment not play dominating role, hides the effect of another kind of color.Abrasive is coated on 51 microns (0.002 inch) thick pet film sheet, and oven drying is placed on white surface then.With the SPM 100 type spectrophotometer/opacimeters of suitable optical filtering (available from Gretag Ltd., Regensdorf, Switzerland) measuring the reflection density of abrasive, and mark the point that reflection density has particular abrasive material color desired value, is 1.32 for cyan (cyan) color promptly.The point that will have the target reflection density then is placed on black hole or the ligh trap.Measure the transparency of this abrasive with the same apparatus of measuring reflection density.Transparence value is high more, and pigment disperses well more in the abrasive.

Granularity and transparency measured value are listed in the table 8.Number average particle size reduces to the pigment particles that 0.2 micron explanation major part is dispersed into independent dispersion after 3 circulations.The transparency measured value that improves constantly in 17 circulations shows has eliminated remaining basically.

Table 8

Circulation is to the influence of number average particle size and transparency

Circulation	????Macrotrac TMMn (micron)	PCS Zave (micron)	Transparency
				????0	?????1.23
???2.9	?????0.210		????1.880
				???5.7	?????0.189		????1.952
???17.1	?????0.202	?????0.223	????2.069
				???34.3		?????0.246	????2.100
???42.9		?????0.219	????2.086

Embodiment 8

Prepare silver halide-behenic acid silver dispersions as follows, promptly earlier in 65.7 parts of 2-butanone and 16.4 parts of toluene, add 15.1 parts and press United States Patent (USP) 3,839, silver halide-behenic acid silver (mol ratio 9:91) dry soaps and 2.8 parts of BUTVAR that step described in 049 prepares ^TMB-79 (available from a kind of resin of Monsanto Company) allows mixture soak 12 hours; Use SILCERSON ^TMThe powerful laboratory of L2AIR type mixing emulsifier (available from Silverson Machines, Ltd) stirred 2 hours, till forming uniform sizing material.Slurry is joined in the loading hopper, be forced into 134MPa (19500psi) with hydraulic pump then, and make it pass through two continuous injection percussion devices, the throttle orifice internal diameter of second injection percussion device sprays the throttle orifice internal diameter of percussion device less than first.The throttle orifice internal diameter is respectively 0.56 millimeter (0.022 inch) and 0.46 millimeter (0.018 inch).Flow velocity maintains 3.8 liters/minute.Use Microtrac ^TMMeasure initial slurry and the granularity by a disposed slurry in spraying percussion device.

The measured value of granularity is illustrated in the table 9.Handling once the equal granularity of back body reduces to 1.2 microns and size distribution from 20.8 microns and shows that granule is clashed into into the granules of pigments of independent dispersion basically.

Table 9

Circulation is to the influence of equal granularity of body and size distribution

Circulation	Microtrac TMMv (micron)	10% particle volume	50% particle volume	90% particle volume
					??0	????20.79	????0.51	?????0.51	?????57.68
??1	????1.18	????0.54	?????0.54	?????1.83

Embodiment 9

Except using different process conditions and not comprising and prepare silver halide-behenic acid silver dispersions by embodiment 8 described methods basically the injection apparatus of bump.Slurry is joined in the loading hopper, be forced into 28MPa (4000psi) with pulsometer then, and make it pass through two continuous injection apparatus, the throttle orifice internal diameter of second injection apparatus is less than the throttle orifice internal diameter of first injection apparatus.The throttle orifice internal diameter is respectively 0.76 millimeter (0.030 inch) and 0.25 millimeter (0.010 inch).Flow velocity maintains 400 ml/min.Use Microtrac ^TMMeasure initial slurry and the granularity by a disposed slurry in injection apparatus.

The measured value of granularity is illustrated in the table 10.Handling once the equal granularity of back body reduces to 5.6 microns and size distribution from 20.8 microns and shows that granule becomes the granules of pigments of independent dispersion in large quantities.

Table 10

Circulation is to the influence of equal granularity of body and size distribution

Circulation	Microtrac TMMv (micron)	10% particle volume	50% particle volume	90% particle volume
					??0	????20.79	????0.51	????0.51	????57.68
??1	????5.60	????0.27	????0.74	????4.91

Embodiment 10

In with 1N hydrochloric acid pH being adjusted to 3 water, add the Sumitomo AKP-50 aluminium oxide of different amounts (available from Sumitomo Chemical Company, New, York, NY), then respectively GardnerDispermat F105 (available from BYK-Gardner, Inc., Silver Spring, MD) mix in, prepare three kinds of abrasive slurries.Oxidation aluminium paste A contains 63 weight portions (30 parts by volume) aluminium oxide and 37 weight portions (70 parts by volume) pH3 water, oxidation aluminium paste B contains 73 weight portions (40 parts by volume) aluminium oxide and 27 weight portions (60 parts by volume) pH3 water, and oxidation aluminium paste C contains 80 weight portions (50 parts by volume) aluminium oxide and 20 weight portions (50 parts by volume) pH3 water.Each slurry is handled with similar methods.In loading hopper, add about 250 milliliters slurry, slurry A is forced into about 172MPa (25000psi), slurry B is forced into about 183MPa (26500psi), slurry C is forced into about 186MPa (27000psi) with pulsometer with pulsometer with pulsometer.Make it pass through three continuous injection percussion devices, each sprays the throttle orifice internal diameter of the throttle orifice internal diameter of percussion device less than previous injection percussion device.The throttle orifice internal diameter is respectively 0.46 millimeter (0.018 inch), 0.30 millimeter (0.012 inch) and 0.23 millimeter (0.009 inch).The fixedly free distance that uses is 1.27 millimeters (0.05 inches).The flow velocity of slurry A maintains about 150 ml/min, and the flow velocity of slurry B maintains about 130 ml/min, and the flow velocity of slurry C maintains about 125 ml/min.Each slurry is cycled through this percussion device series, turn back to loading hopper then, carry out 18 circulations altogether.Take out 2 milliliters of samples since the 2nd circulation by different intervals.Percussion device is immersed in the mixture of ice and water, makes slurry temperature (with the thermometer measure that is placed in the loading hopper) remain on 45-55 ℃.Use Microtrac ^TMMeasure the granularity of each sample.

The granulometry value of slurry A, B and C is listed in respectively in the table 1,2 and 3.The continuous minimizing of the equal granularity of body shows that granule is reduced to the pigment particles of independent dispersion in large quantities.

Table 11

Circulation is to the influence of equal granularity of the body of slurry A and size distribution

Circulation	Microtrac TMMv (micron)	10% particle volume	50% particle volume	90% particle volume
					???0	????1.89	?????0.21	????0.31	?????1.32
???3	????1.03	?????0.36	????0.88	?????1.78
					???6	????1.29	?????0.49	????1.12	?????2.38
???12	????0.55	?????0.20	????0.25	?????1.17
					???18	????0.58	?????0.20	????0.29	?????1.21

Table 12

Circulation is to the influence of equal granularity of the body of slurry B and size distribution

Circulation	??Microtrac TMMv (micron)	10% particle volume	50% particle volume	90% particle volume
					???0	?????1.03	?????0.15	?????0.42	?????2.23
???3	?????0.78	?????0.16	?????0.26	?????1.80
					???6	?????0.58	?????0.14	?????0.25	?????1.25
???12	?????0.59	?????0.19	?????0.24	?????1.31
					???18	?????0.51	?????0.14	?????0.24	?????1.10

Table 13

Circulation is to the influence of equal granularity of the body of slurry C and size distribution

Circulation	Microtrac TMMv (micron)	10% particle volume	50% particle volume	90% particle volume
					???0	????1.89	?????0.51	?????1.37	?????3.08
??2.5	????1.17	?????0.32	?????0.99	?????2.13

The assessment of spray printing printing ink

The printing ink that adds pigment has good light resistance and durability, and should contain less granule in order to obtain satisfactory performance.In addition, usedly during spray printing add pigment ink and should be able to prevent conglomeration again in a long time, in order to avoid stop up the ink nozzle of ink jet printers.The long-term impressionability of spray printing printing ink can assess 1 with one of following two kinds of methods) not too strict colour bar test and 2) stricter whole box life test.In two tests, the about 40 milliliters spray printing printing ink that add pigment are contained in the HP51626A ink cartridge, again ink cartridge are contained in the Nova Jet II type deep fat ink-jet printing machine (available from Encad in San Diego, CA).In the colour bar test, being 1.9 centimetres wide with four-way mode (4pass-mode) printing length is 86 centimetres solid blocky appearance, and the time interval of printing was 0,0.5,1,2,4,6,10,12 and 16 weeks.Test is performed until print quality and begins to reduce and observe till the tangible striped.The final time interval of satisfied print quality observed in record then.In whole box life test, print the solid blocky appearance of 86 centimetres wide of 91 centimeter length, all printing ink in box are consumed or print quality begins till the variation.Before ink cartridge used up, the solid image that 40 milliliters of spray printing printing ink is printed by the four-way mode was generally the 180-230 centimeter length.Outcome record for (whole print image piece has uniform color density, and does not observe striped) well, in (printing ink is printable, but observes some stripeds), poor (printing ink is printable, but observes a lot of stripeds) and very poor (printing ink can not be printed).The butyl amide (MW861) of the two azlactones of preparation

In 946 milliliters of (32oz.) glass jars, put into 138 gram Bayer aspartate XP7059E (available from TheBayer Co., Pittsburgh, PA) and 84 gram vinyl-dimethyl base azlactones (available from SNPE Co., Princeton, NJ).With this glass jar sealing, and in 65 ℃ of air circulation ovens, placed 3 days.Take out glass jar then from baking oven, cooling is opened.In 30 minutes, add 44 gram n-butylamines in batches.With the glass jar sealing, put back in 65 ℃ of baking ovens, spend the night.Take out glass jar again from baking oven, cooling is opened.Add 200 milliliters of ethanol and 230 milliliters of 5N NaOH.Glass jar is placed in the steam bath heats, the short time stirred reaction mixture is till the reactant mixture dissolving.Allowing reactant mixture at room temperature place then spends the night.Most ethanol are fallen in decompression distillation then, with three parts 250 milliliters remaining ethanol of ethyl acetate extraction.Vapourisation under reduced pressure falls all remaining organic solvents in the aqueous solution again.The water that adds capacity, two azlactone butyl amide (butylamide ofbis-azlactone) 50% aqueous solution (MW861) of preparation.

Comparative Examples 1

Condensed water dispersion (Sun Magenta QHD-6040 by magenta pigment, available from Sun Chemical Corp., Cincinnati, OH, solids content is 39%), condensed water dispersion (the Sun YellowYGD-8851 of yellow uitramarine, solids content is 36%), four kinds of ink-jet inks that add pigment of condensed water dispersion (Sun LHD-9303, solids content is 49%) preparation of the condensed water dispersion (Sun Cyan BCD-9941, solids content is 45%) of green pigment or black pigment.Each preparation method who adds the pigment ink-jet ink is according to the elder generation of the umber described in the table 4 water (with 1NaOH the pH value being adjusted to 9), uses 0.1 part of SURFYNOL then ^TMDF-58 (available from Air Products and Chemicals, Inc., Allentown, a kind of defoamer of PA) dilutes pigment dispersion, is the SILVERSON of 2000rpm simultaneously with rotating speed ^TMAgitator stirs dispersion 5 minutes.Further stirring the mixture 10 minutes the time, add diethylene glycol (DEG) (DEG) gradually then.When adding DEG, monitor the pH value of mixture, it is maintained 9 with 1N NaOH.

Table 14

Pigment type	The dispersion umber	The moisture content number	The DEG umber
				Sun?Magenta?QHD-6040	????41	????128	????230
Sun?Yellow?YGd-8851	????44	????125	????230
				Sun?Cyan?BCD-9941	????35	????134	????230
Sun?Black?LHD-9303	????33	????137	????230

Make this ink mixture by 5 microns Whatman Polycap, 36 HD filters then, and the assessment colour bar is printed test mass on Novajet II thermal ink jet printers.Print result is listed in the table 15, this result show spray ink degree of scatter for the first time colour bar print test and also do not pass through.

Table 15

Pigment type	Time (week)
		Sun?Magenta?QHD-6040	????＜0.5
Sun?Yellow?YGd-8851	????＜0.5
		Sun?Cyan?BCD-9941	????＜0.5
Sun?Black?LHD-9303	????＜0.5

Comparative Examples 2

Four kinds of ink-jet inks that add pigment of method preparation by Comparative Examples 1 further process then.For each pigment, allow about 400 milliliters ink under 55MPa (8000psi) pressure, pass through 15-15MR-STBA type homogenizer (available from APV Gaulin Inc.), circulate, till ink is altogether on average by 4 times.The end temperature of ink is about 85 ℃.With ink filter, be contained in the ink cartridge then, measure the colour bar test period.Print result is listed in the table 6, this result show spray ink degree of scatter for the first time colour bar print test and also do not pass through.

Table 16

Pigment type	Time (week)
		Sun?Magenta?QHD-6040	????＜0.5
Sun?Yellow?YGd-8851	????＜0.5
		Sun?Cyan?BCD-9941	????＜0.5
Sun?Black?LHD-9303	????＜0.5

Embodiment 11

Four kinds of ink-jet inks that add pigment of method preparation by Comparative Examples 1 further process then.For each pigment, about 250 milliliters of inks are added in the loading hopper, be forced into 69-103MPa (10000-15000psi) with pulsometer, (the seam height is 400 microns to allow it pass through an interaction chamber (interactive chamber) H230Z then, available from Microfluidics International Corp., Newton, MA), again by an interaction chamber H210Z (the seam height is 200 microns, available from Microfluidics International Corp.).Flow velocity maintains 400 ml/min, allows ink circulation pass through two interaction chambers, 10 times altogether.With cold water ink temperature is remained on 55 ℃.With ink filter, the ink cartridge of packing into is measured colour bar time and whole box life-span then.Print result is listed in the table 17, and this result shows that ink-jet ink has been disperseed some when the interaction chamber that ink is successively decreased by slit continuously.

Table 17

Pigment type	Time (week)	Ink cartridge
			Sun?Magenta?QHD-6040	????1	Medium
Sun?Yellow?YGd-8851	????2	Good
			Sun?Cyan?BCD-9941	????1	Medium
Sun?Black?LHD-9303	????1	Medium

Embodiment 12

Four kinds of ink-jet inks that add pigment of method preparation by Comparative Examples 1 further process then.For each pigment, about 250 milliliters of inks are added in the loading hopper, be forced into 159-172MPa (23000-25000psi) with pulsometer, allow it pass through three continuous injection percussion devices then, each sprays the throttle orifice internal diameter of the throttle orifice internal diameter of percussion device less than previous injection percussion device.The throttle orifice internal diameter is respectively 0.46 millimeter (0.018 inch), 0.30 millimeter (0.012 inch) and 0.23 millimeter (0.009 inch).The fixedly free distance that uses is 1.27 millimeters (0.05 inches).Flow velocity maintains about 400 ml/min.Ink mixture is cycled through this percussion device series, turn back to loading hopper then, carry out 10 circulations altogether.Percussion device is immersed in the mixture of ice and water, makes the temperature (with the thermometer measure that is placed in the loading hopper) of ink mixture be about 45 ℃.With ink filter, be contained in the ink cartridge then, measure colour bar time and whole box life-span.Print result is listed in the table 18, and this result shows that ink-jet ink disperses finely when the percussion device of the polyphone that reduces step by step with the throttle orifice diameter is handled.

Table 18

Pigment type	Time (week)	Ink cartridge
			Sun?Magenta?QHD-6040	?????6	Good
Sun?Yellow?YGd-8851	?????＞16	Good
			Sun?Cyan?BCD-9941	?????12	Difference
Sun?Black?LHD-9303	?????12	Medium

Embodiment 13

Four kinds of ink-jet inks that add pigment of method preparation by Comparative Examples 1 further process then.For each pigment, about 250 milliliters of inks are added in the loading hopper, be forced into 159-172MPa (23000-25000psi) with pulsometer, allow it pass through three continuous injection apparatus then, the throttle orifice internal diameter of each injection apparatus is less than the throttle orifice internal diameter of previous injection apparatus.The throttle orifice internal diameter is respectively 0.46 millimeter (0.018 inch), 0.30 millimeter (0.012 inch) and 0.23 millimeter (0.009 inch).Flow velocity maintains about 400 ml/min.Ink mixture is cycled through this percussion device series, turn back to loading hopper then, carry out 10 circulations altogether.Percussion device is immersed in the mixture of ice and water, makes the end temperature (with the thermometer measure that is placed in the loading hopper) of ink slurry be about 45 ℃.With ink filter, be contained in the ink cartridge then, measure the whole box life-span.Print result is listed in the table 19, and this result shows that ink-jet ink disperses finely when the percussion device of the polyphone that successively decreases with the throttle orifice diameter is handled.

Table 19

Pigment type	Distance (centimetre)
		Sun?Magenta?QHD-6040	Good
Sun?Yellow?YGd-8851	Good
		Sun?Cyan?BCD-9941	Difference
Sun?Black?LHD-9303	Difference

Embodiment 14

Prepare the graining paste concentrate as follows, promptly add 86.5 parts of SUNFAST in the 200 portions of diethylene glycol (DEG)s (DEG) in being contained in a container earlier ^TMBlue 15: 3 (green pigment cake of press, the concentration of pigment in water is 50%, available from Sun Chemical Co.), two azlactone resin (MW861) aqueous solution of 25 part 50% butyl amide, 15 parts of CT-136 (available from a kind of surfactant of Air Products Co.) and 50 parts of water.Then at SILVERSON ^TMModel L2 AIR starches with hybrid pigment in the mixing emulsifier in powerful laboratory.Rotating speed with 500rpm stirred 5 minutes earlier, and the rotating speed with 2000rpm stirred 10 minutes then, did not observe precipitation in the bottom of container at last.The graining paste concentrate washs with 30 parts of other water, about 250 milliliters of graining paste concentrates are added in the loading hopper, be forced into 83-90MPa (12000-13000psi) with pulsometer, allow it pass through an interaction chamber H230Z (the seam height is 400 microns) then, again by an interaction chamber H210Z (the seam height is 200 microns).Flow velocity maintains 400 ml/min, allows the graining paste concentrate cycle through two interaction chambers, 24 times altogether.With being immersed in the final temperature (with the thermometer measure that is placed in the loading hopper) that makes ink mixture in ice and the aqueous mixtures as the chamber mutually is 45 ℃.

Except the pH value is remained on 8, in the graining paste concentrate, add entry and DEG by Comparative Examples 1 described similar approach, prepare about 400 milliliters of ink-jet inks.Then ink-jet ink is filtered, the ink cartridge of packing into is measured the whole box life-span.The whole box life-span is medium.

Embodiment 15

Except under different conditions, allowing the graining paste concentrate by spraying percussion device, rather than by beyond the interaction chamber, prepare a kind of ink-jet ink by the method for embodiment 14.About 250 milliliters of graining paste concentrates are added in the loading hopper, be forced into 138-172MPa (20000-25000psi) with pulsometer, allow it pass through three continuous injection percussion devices then, each sprays the throttle orifice internal diameter of the throttle orifice internal diameter of percussion device less than previous injection percussion device.The throttle orifice internal diameter is respectively 0.46 millimeter (0.018 inch), 0.30 millimeter (0.012 inch) and 0.23 millimeter (0.009 inch).The fixedly free distance that uses is 1.27 millimeters (0.05 inches).Flow velocity maintains about 400 ml/min.The graining paste concentrate is cycled through this percussion device series, turn back to loading hopper then, carry out 24 circulations altogether.Percussion device is immersed in the mixture of ice and water, makes the end temperature (with the thermometer measure that is placed in the loading hopper) of ink mixture be about 45 ℃.Prepare ink-jet ink by the graining paste concentrate then,, be contained in the ink cartridge, measure the whole box life-span its filtration.The whole box life-span is good.

Embodiment 16

Except under different conditions, allowing the graining paste concentrate by injection apparatus, rather than by spraying beyond the percussion device, prepare a kind of ink-jet ink by the method for embodiment 14.About 250 milliliters of graining paste concentrates are added in the loading hopper, be forced into 159-172MPa (23000-25000psi) with pulsometer, allow it pass through three continuous injection apparatus then, the throttle orifice internal diameter of each injection apparatus is less than the throttle orifice internal diameter of previous injection percussion device.The throttle orifice internal diameter is respectively 0.46 millimeter (0.018 inch), 0.30 millimeter (0.012 inch) and 0.23 millimeter (0.009 inch).Flow velocity maintains about 400 ml/min.The graining paste concentrate is cycled through this injection apparatus series, turn back to loading hopper then, carry out 24 circulations altogether.Percussion device is immersed in the mixture of ice and water, makes the end temperature (with the thermometer measure that is placed in the loading hopper) of graining paste concentrate be about 45 ℃.Prepare ink-jet ink by the graining paste concentrate then,, be contained in the ink cartridge, measure the whole box life-span its filtration.The whole box life-span is good.

Embodiment 17

This experiment shows the advantage of the throttle orifice device of exit energy free vibration.Used dispersion contains 12.4% weight percent carbon black and 7% weight nitrocellulose in THF, be benchmark with the gross weight of dispersion.The injection percussion device has the bump chamber of 8 polyphones.Earlier dispersion is sprayed impact system by one, this system comprises the bump chamber that a throttle orifice outlet basically can not free vibration.Specifically, the distance that exports from the throttle orifice supporting-point to the throttle orifice device of this throttling pore chamber is 0.0375 inch (0.09525 centimetre).The distance that the throttle orifice device exports to rum point is 0.03 inch (0.0762 centimetre).Ratio=12.5.Then identical dispersion is sprayed impact system by second, but this system comprises the throttle orifice outlet bump chamber of free vibration basically.Specifically, the distance of this throttling pore chamber from throttle orifice device supporting-point to throttle orifice device outlet is 0.0375 inch (0.09525 centimetre).The distance that the throttle orifice device exports to rum point is 0.0275 inch (0.06985 centimetre).Ratio=13.6.Dispersion is reduced to 30000psi by the stagnation pressure of these two systems, and the pressure drop of clashing at last on the chamber is variable or is 17500psi.Serious wearing and tearing only just took place in fixing nozzle after 30 minutes.Nozzle not wearing and tearing basically after long-time operation freely.

Claims (28)

1. manufacture method that contains the dispersion of solvent and hard inflexibility particle, this method comprises the steps:

A) dispersion components is mixed into the diffusing mixture of half point;

B) to this mixture pressurization; And

C) make pressurised mixt pass through the series of forming by two bump chamber devices at least, wherein mixture is divided at least two liquid streams, make each liquid stream by comprising the throttle orifice device of the little throttle orifice of be with internal diameter, and each liquid stream clash into mutually when leaving the throttle orifice device

The throttle orifice internal diameter of first bump chamber device is greater than the throttle orifice internal diameter of last bump chamber device.

2. the method for claim 1 is characterized in that being no more than to the distance of rum point from the liquid flow export of throttle orifice device the twice of throttle orifice diameter.

3. the method for claim 1 is characterized in that the outlet of throttle orifice device can free vibration.

4. the method for claim 1 is characterized in that described particle is a magnetic paint.

5. the method for claim 1 is characterized in that the pressure drop of clashing on the chamber device series is at least 205MPa.

6. the method for claim 1 is characterized in that described dispersion also comprises polymer adhesive.

7. the method for claim 1 is characterized in that this method comprises that also the dispersion that at least a portion was handled pressurizes again and make it cycle through the step of bump chamber device series.

8. the method for claim 1 is characterized in that in the step c) mixture being divided into two liquid flows, and makes described liquid stream bump mutually by the angles of 180 degree.

9. the method for claim 1 is characterized in that making in the step c) liquid stream by also comprising the throttle orifice device of an extension.

10. the method for claim 1 is characterized in that the speed that liquid flows by throttle orifice in the step c) is at least 300 meter per seconds.

11. the method for claim 1 is characterized in that making in the step c) described mixture by 3 to 9 bump chamber devices.

12. the method for claim 1, it is characterized in that making in the step c) described liquid stream is the cylindrical throttle orifice of 0.1-1.0 millimeter by internal diameter.

13. the method for claim 1, the content that it is characterized in that hard inflexibility particle in the dispersion is up to 50% volume.

14. method as claimed in claim 4, the content that it is characterized in that magnetic paint is 20-50% weight.

15. device, it comprises the polyphone bump chamber that connects behind high-pressure pump and at least two, each bump chamber comprises that (i) is divided into the inlet manifold of two or more independent liquid streams, the outlet manifold that (ii) will mix again by the independent liquid stream bump ground of throttle orifice device and the (iii) interface channel between at least two inlet manifold and outlet manifold with pressurized fluid stream in the bump chamber, and the throttle orifice internal diameter in first bump chamber is greater than the throttle orifice internal diameter in last bump chamber.

16. device as claimed in claim 15 is characterized in that described pump can apply the pressure of 205MPa at least.

17. device as claimed in claim 15 is characterized in that the distance from the throttle orifice device to bump center, chamber is no more than the twice of throttle orifice diameter.

18. device as claimed in claim 15 is characterized in that described throttle orifice device can free vibration.

19. device as claimed in claim 15 is characterized in that described throttle orifice makes by being selected from following one group material: synthetic sapphire, tungsten carbide, diamond, stainless steel and ceramic material.

20. device as claimed in claim 15 is characterized in that described throttle orifice has circle, hexagon or oval-shaped hole.

21. device as claimed in claim 15 is characterized in that described throttle orifice is columniform, its internal diameter is the 0.1-1.0 millimeter.

22. device as claimed in claim 15 is characterized in that described throttle orifice device also has an extension.

23. device as claimed in claim 15 is characterized in that pressure sensor is contained on the interface channel, so that detect the wearing and tearing or the obstruction of throttle orifice.

24. the method for claim 1 is characterized in that described blend step is included in the duplicate rows star blender to major general's pigment and a part of solvent, adds remaining solvent then at least.

25. method as claimed in claim 24 is characterized in that mixing the back and adds polymer adhesive in duplicate rows star blender.

26. a manufacture method that contains the dispersion of solvent and hard inflexibility particle, this method comprises the steps:

A) dispersion components is mixed into the diffusing mixture of half point;

B) to this mixture pressurization; And

C) make pressurised mixt pass through a series of throttle orifices, the diameter of each throttle orifice is less than the diameter of previous throttle orifice.

27. a device that is used to make the dispersion that contains solvent and hard inflexibility particle is characterized in that this device comprises:

A) high-pressure pump and

B) throttle orifice that successively decreases of a series of diameters.

28. the method for claim 1 is characterized in that described hard inflexibility particle is a coloring pigment.

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