A pneumatic control system for providing pressurized air and vacuum to ophthalmic microsurgical instruments. The pneumatic system is constructed in a drawer assembly to allow it to be readily inserted into or removed from a modularly constructed cabinet of a microsurgical control console.. In addition, the pneumatic system improves upon existing pneumatic control systems by providing a third mode of microscissors operation from a single pneumatic port. The third mode is made possible by a high speed three-way solenoid control valve which provides rapid pulses of air to the pneumatic port.. A second improvement involves the use of a pneumatic pressure transducer to monitor pneumatic pressure being supplied to the pneumatic system in order to recognize non-hazardous transient drops in air pressure which can occur under certain normal operating conditions. A third improvement relates to the use of an intraocular pressure accumulator downstream from a final solenoid-operated pinch valve, which reduces fluctuations in air pressure and has other advantages.

1. Cross-Reference to Related Applications
The present invention is related to the subject matter of the following commonly assigned co-pending application Ser. No. 07/267,713 filed Nov. 4, 1988, which is a continuation of application Ser. No. 06/928,170 filed Nov. 6, 1986 and entitled "Control System For ophthalmic Surgical Instruments."
The present invention is related to the subject matter of the following commonly assigned applications being filed concurrently on even date herewith:
Application Serial No. (Attorney Docket No. 4569-00091) entitled "Control System For Ophthalmic Surgical Instruments";
Application Serial No. (Attorney Docket No. 4569-00092) entitled "Control System For Calibrating And Driving Ultrasonic Transducer";
Application Serial No. (Attorney Docket No. 4569-00093) entitled "Remote Control Console For Surgical Control System";
Application Serial No. (Attorney Docket No. 4569-00094) entitled "Vitrectomy Probe";
Application Serial No. (Attorney Docket No. 4569-00095) entitled "Modular Cabinet For Surgical Control Systems";
Application Serial No. (Attorney Docket No. 4569-00096) entitled "Footswitch Assembly With Electrically Engaged Detents;" and
Application Serial No. (Attorney Docket No. 4569-00097) entitled "Motorized IV Pole Assembly."
The disclosures of each and every one of the above-referenced applications is hereby incorporated herein by reference.
2. Field of the Invention
The present invention relates in general to pneumatic control circuits and systems for providing controlled levels of pressurized air or vacuum to instruments used during ophthalmic microsurgical procedures, and in particular to improvements in such pneumatic circuits and to a method of modularly constructing such pneumatic circuits within a drawer assembly.
3. Description of Related Art
In the ophthalmic microsurgical arts, a number of different procedures which require pressurized air or vacuum are known. For example, aspiration, that is providing suction via a controlled vacuum level, is used widely for various procedures and with various instruments. Aspiration is used, for example, during the engagement, stripping and removal of residual lens cortical material in extra-capsular cataract extraction and phacoemulsification procedures. Phaco-fragmentation procedures also make use of aspiration. Anterior and posterior vitrectomies also require aspiration for the removal of cut material from the eye, such as vitreous.
Intraocular pressure (IOP) control provides precisely adjusted delivery of filtered air to the eye during posterior ocular pressure procedures. Also, the IOP system can be used to pressurize an irrigation supply of balanced salt solution for the eye during anterior segment procedures. Microscissors are another ophthalmic microsurgical instrument which are often pneumatically driven. Three different scissor drive modes are known today: single cut mode, variable rate cut mode, and proportional cut mode.
While a variety of pneumatic systems are known for providing the appropriate pressurized air or vacuum signals required for the aforementioned microsurgical procedures or instruments, there nevertheless remains an interest in improving the quality of operation of these devices and making such pneumatic control systems (1) more powerful, in terms of the number of functions supported, (2) more accurate in the sense of precisely providing the desired pneumatic pressure or vacuum signals, and (3) easier and simpler to service and/or repair when necessary.
The assignee of the present invention, namely Storz Instrument Co. of St. Louis, Mo. (hereinafter "Storz"), has marketed an ophthalmic microsurgical system under the trademark "DAISY" which is housed in a single control console and which supports all the pneumatic functions described above, except for (1) pressurizing an irrigation supply for anterior segment procedures, and (2) multi-cut scissors mode. It is one object of the present invention to provide all of the foregoing pneumatic functions, including the two last mentioned, in a manner that satisfies the three aforementioned interests.
The DAISY console, a pressure switch is used to monitor the incoming air pressure of the main supply line that provides air to the pneumatic system. The purpose of pressure switch is to detect abnormally low air pressure conditions which can exist, for example, if the hospital air supply pressure falls beneath expected levels or if some other problem interrupts the air supply to the DAISY console. In the DAISY console, this pressure switch is set to trip out at an appropriate level, such as 80 psig. Through experience with the DAISY pneumatic system, it has been found, that under certain transient conditions, namely low but acceptable pressure levels from the hospital supply line when user requests for high vacuum levels are initiated, demand for the pressurized air momentarily outstrips the ability of the hospital line to supply same on account of very brief delays in pressurized air movement. Such transient conditions on occasion cause the pressure switch to indicate that the air pressure is low, at which time the microsurgical console warns the surgeon of the low air supply condition. However, study has shown that such transient conditions, if of sufficiently short duration, are non-hazardous and the surgeon need not be warned or otherwise interrupted. Thus it is an object of the present invention to provide a pneumatic control system which can handle non-hazardous transient air pressure drops, which still recognizing and correctly responding to transient air pressure drops which do indicate that a warning to the surgeon of the low air pressure condition is required or desirable.
With advances in ophthalmic microsurgical techniques, there is increasing interest and need for a highly accurate IOP system which is capable of delivering controlled low pressure air with a minimum amount of pulsations or other variations in pressure. IOP systems typically operate in the range of 0 to 100 mmHg. At these pressure levels, it has not been possible previously, using on/off solenoid control valves, to ramp up air pressure to a desired setting in this range without overshoot. Further, in prior art IOP systems, there is a discernable variation in the output pressure of the IOP system from the desired pressure setting by as much as plus or minus four mmHg or more. Thus, is an object of the present invention to provide an IOP system which uses inexpensive on/off solenoid control valves, and yet still avoids overshoot and minimizes pressure variations from the desired IOP setting.

Pneumatic controls for ophthalmic surgical system


An epilating apparatus has a cylindrical rotating cylinder, a plate and driving portions. The cylindrical rotating cylinder has a plurality of claw portions for epilation. The plate has a plurality of openings, in which the plurality of claw portions are exposed, and covers the outside exposed surface of the rotating cylinder. The driving portions open-close drives the plurality of claw portions while rotationally drives the rotating cylinder so that hairs held by the claw portions are pulled out. The claw tip shape of each claw portion is formed in the shape of a circular arc having a center at the rotational center vicinity of the rotating cylinder.

1. Field of the Invention
The present invention relates to an epilating apparatus, and in particular, it relates to an epilating apparatus used to extract body hair for beautification and like.
2. Description of the Related Art
Heretofore, an epilating apparatus has been known, which has a plurality of claws for epilation that is open-close driven on a cylindrical rotating cylinder that is rotationally driven. This epilating apparatus nips hair by the claw portions provided on the rotating cylinder, and pulls out the nipped hair by the rotation of the rotating cylinder to perform an epilating process.
In the epilating apparatus, there has been a problem that the rotating cylinder and the claw portion are directly brought into contact with the skin, thereby harming the skin. To solve this problem, as shown in FIG. 1 or FIG. 2, an epilating apparatus is proposed which has a structure where a the skin protection plate 94 is provided so as to cover the outside exposed surface of a rotating cylinder 8, and a claw portion 5 comprising a movable claw 86 and a fixed claw 88 is exposed from a plurality of opening portions 94a formed in this plate 94 (for example, see Japanese Unexamined Patent Application Laid-open No. 2003-47521).
However, the epilating apparatus is devised such that the removable claw 86 nips the hair in a state inclined to the fixed claw 88, and hence, any of claw tip portions of the movable claw 86 and the fixed claw 88 which are portions to nip the hair is linearly formed. In contrast, since the skin protection plate 94 has a shape bent in a reverse U letter, as shown in FIG. 2, there develops a gap d between the claw tip portions of the movable claw 86 and the fixed claw 88 and the top portion of the plate 94. That is, while the epilating apparatus comprises the plate 94 so as to be able to protect the skin, since there exists the gap d between the plate 94 and the claw portion 5, it is difficult to nip a particularly short hair and perform epilating process, and further, even if it is a long hair, it is difficult to nip the hair from the root. Therefore, there is a problem that irritation during the epilating process becomes strong.


A first contact, a second impurity region, and a second low-concentration impurity region form a Schottky barrier diode. The second impurity region has the same impurity concentration as those of first impurity regions, and thus can be formed in the same process as forming the first impurity regions. In addition, the second low-concentration impurity region has the same impurity concentration as those of first low-concentration impurity regions, and thus can be formed in the same process as forming the first low-concentration impurity regions.

1. Technical Field
The present invention relates to a semiconductor device, and to a technique applicable to, for example, a semiconductor device having a diode.
2. Related Art
Rectifying devices are often used in an electric circuit. In semiconductor devices, diodes such as a Schottky barrier diode are often used as rectifying devices.
Schottky barrier diodes formed using a semiconductor substrate include, for example, a diode disclosed in Japanese Unexamined Patent Publication No. H05-55553, A Schottky barrier diode disclosed in Japanese Unexamined Patent Publication No. H05-55553 is configured such that an n+ region is formed in a portion of the surface layer of an n region, and an electrode is connected to each of the n+ region and the n region. In Japanese Unexamined Patent Publication No. H05-55553, the Schottky barrier diode is formed together with a bipolar transistor. The n region of the Schottky barrier diode is formed to have the same depth as that of a well.
In addition, Japanese Unexamined Patent Publication No. H09-55439 and Japanese Unexamined Patent Publication No. H10-28045 disclose semiconductor devices in which a MOS transistor and a Schottky barrier diode are formed together. Particularly, Japanese Unexamined Patent Publication No. H09-55439 discloses that a silicide is used as a Schottky electrode. In addition, Japanese Unexamined Patent Publication No. H10-28045 discloses that an n region is caused to be adjacent to an n+ region serving as a source or a drain of the MOS transistor, and that a Schottky electrode is connected to the n region.
In addition, Japanese Unexamined Patent Publication No. 2010-147387 and Japanese Unexamined Patent Publication No. 2011-243978 disclose that in compound semiconductor devices using two-dimensional electron gas, a Schottky electrode is provided in a region which is located between a gate electrode and drain in an electron supply layer, and that the Schottky electrode is electrically connected to a source.
Further, a non-patent document (S. Snakaran et al., J. Solid-State Circuit, 42, P. 1058, 2007) discloses that an element isolation film is located between two electrodes of a Schottky barrier diode.
Meanwhile, Japanese Unexamined Patent Publication No. 2005-175063 discloses that in a transistor including an n-type drift region, the transistor has a high withstanding voltage by providing a p-type impurity layer in the surface layer of a drift region.

This patent is subject to a terminal disclaimer.


An associative memory with an invert result capability to allow the identification of an entry as being matched when an entry or portion thereof is specifically not matched is disclosed (or alternatively viewed as an entry or portion thereof indicated as matched when it actually was not matched). One such associative memory typically includes multiple associative memory entries, each of which typically includes storage for one or more subsets of bits to be used in matching a lookup value and for one or more invert result indications to identify whether or not corresponding particular subsets of the one or more subsets of bits are to be inverted in producing an entry match result. Result generation logic is used to identifying the entry match result based on a comparison of the one or more subsets of bits with the lookup value and responsive to the one or more invert result indications to invert an intermediate comparison result for the one or more subsets of bits as indicated by the one or more invert result indications.

The communications industry is rapidly changing to adjust to emerging technologies and ever increasing customer demand. This customer demand for new applications and increased performance of existing applications is driving communications network and system providers to employ networks and systems having greater speed and capacity (e.g., greater bandwidth). In trying to achieve these goals, a common approach taken by many communications providers is to use packet switching technology. Increasingly, public and private communications networks are being built and expanded using various packet technologies, such as Internet Protocol (IP). Note, nothing described or referenced in this document is admitted as prior art to this application unless explicitly so stated.
A network device, such as a switch or router, typically receives, processes, and forwards or discards a packet based on one or more criteria, including the type of protocol used by the packet, addresses of the packet (e.g., source, destination, group), and type or quality of service requested. Additionally, one or more security operations are typically performed on each packet. But before these operations can be performed, a packet classification operation must typically be performed on the packet.
Packet classification as required for, inter alia, access control lists (ACLs) and forwarding decisions, is a demanding part of switch and router design. The packet classification of a received packet is increasingly becoming more difficult due to ever increasing packet rates and number of packet classifications. For example, ACLs typically require matching packets on a subset of fields of the packet header or flow label, with the semantics of a sequential search through the ACL rules. Access control and quality of service features are typically implemented based on programming contained in one or more ACLs. To implement features in hardware, one or more ACL lists are converted to associative memory entries which are programmed into an associative memory for performing matching operations to identify a desired result (e.g., drop, route, etc.) for a packet.
Associative memories are often used in a communications device for implementing the policies specified in ACLs. FIG. 1A shows one prior art associative memory 100 having multiple associative memory entries 102. Programming and lookup signals 101 are used to program associative memory entries 102, as well as to provide a lookup value for comparing to the associative memory entries 102 to generate entries' match results 119. Typically but not always, a priority encoder 120 is included in or with an associative memory to identify a highest priority result 121 from entries' match results 119 which indicate a match was found for a given lookup value. In one embodiment associative memory entries may include binary content-addressable memory entries (e.g., include a value to be compared against), ternary content-addressable memory entries (e.g., include a value and mask used to identify a value to be compared against), or another type of associative memory entries.
FIG. 1B illustrates another prior art associative memory 110 which includes multiple search blocks 112, 114 and 116, each of which typically include a block mask capability to be used to mask each entry (e.g., binary or ternary content-addressable memory entry) within its corresponding block in identifying a value to be compared against the provided lookup value.
FIG. 1C illustrates a typical prior art associative memory entry with comparison logic 140. A value to be compared 142, which typically includes a stored comparison value and possibly a mask (such as in a ternary content-addressable memory) and possibly this result is masked with a block mask. A comparison is made between the lookup value 145 and the value to be compared 142 to identify an entry match result 147 identifying whether there was a match (i.e., a hit) or there was not a match (e.g., a miss). FIG. 1D illustrates part of a typical prior art associative memory entry cell 160. The results of the bit-by-bit comparisons 161–169 are generated based on the lookup value and the value to be compared. A result line 171 is typically used to perform a wired-AND operation. If any one of the bit-by-bit comparison results 161–169 results in a miss (e.g., a low value), the corresponding bit match transistor 174 is turned on and the result line 171 becomes high due to Vcc 180, which produces a miss indication on result signal 185 (which in one embodiment is inverted by inverter 182 to drive the hit/miss indication signal 185); otherwise, a hit indication is produced on result signal 185.
It is common for an ACL entry to specify an address to match, which can usually be converted to a single associative memory entry. However, it is also common to specify every address but a single (or even multiple) addresses in an ACL entry, which causes many associative memory address to be generated. For example, if a ternary content-addressable memory is being used, all entries but a single value typically can be specified in thirty-two entries. This explosion of entries problem can be further compounded when multiple ACL lists are combined into a single set of associative memory entries using one of several well-known techniques. In a product with a limited number of associative memory entries available, a few ACL entries can consume a significant portion or all of the associative memory entries.

Associative memory with invert result capability


A lift arm (9) includes a first arm (11) and a second arm (12). A pivot joint portion (32) where the first arm (11) is pivoted on a bracket (8) stood at a vehicle side portion substantially corresponds to the rear end of an operation control portion. A rod (15) as a swing motion-limiting member is interposed between the bracket (8) and the second arm (12). An angle of bend formed by the first arm (11) and the second arm (12) is set to be large at a lowered position of the lift arm and small at a lifted position.

Conventionally, there is a well-known working vehicle called as a skid steer loader, which can turn on a small circle with driving wheels by operating steering levers provided in an operation control portion so as to carry out loading and dumping work in a limited space. Generally, the skid steer loader is equipped on a side portion thereof with a lift arm, which is formed in an approximate inverse L-shape in a side view, and extended forward from a rear portion of the vehicle. The lift arm can lift up and down a working machine, such as a bucket, attached on a front end of the arm, in the almost vertical direction relative to the ground.
Such a skid steer loader is desired to have a sufficiently long bucket reach when the lift arm is lifted up at an uppermost position. To achieve this request, the vehicle requires a bracket to support the lift arm. The bracket tends to be a big structure so as to have enough strength. A bigger bracket is needed for a longer bucket reach. However, a big bracket sometimes obstructs an operator's rear or side view from the operation control portion so badly that the operator feels difficulty in backing and turning operation of the vehicle.
To solve the above problem, a conventional type skid steer loader is disclosed in JP-Hei6(1994)-33476, in which the operator's side view is improved without increasing the number of needed links.
However, in each of the conventional skid steer loaders, the lift arm, while being lifted up, moves away from the vehicle body so as to have a bad influence on the skid steer loader in its fore-and-aft balance and its loading and dumping work, because the arm is integrally formed between its ends pivoted onto the bracket and the working machine, so as to have a constant angle bend.
Besides, JP-Hei11(1999)-158905 discloses a conventional art relating to a skid steer loader, in which an operator doesn't have to move the vehicle back and forth so much in dumping stuff loaded on a bucket onto a truck etc. Furthermore, according to the document, some other problems are also solved to improve operability of loading and dumping work. For example, the vehicle is prevented from lurching backward when the bucket is being lifted up.
However, the above conventional skid steer loader is configured in such a way that the bucket is positioned at the forefront of the vehicle when the lift arm is lifted up at an uppermost position. Therefore, the vehicle tends to lose balance in dumping stuff loaded on the bucket onto a truck etc.
JP-2001-64990 discloses a skid steer loader which is equipped with a slidable arm on a main arm of a lift arm. The slidable arm is slidable against the main arm so that a bucket provided thereon should move on a demanded locus, such as a vertical line, a circular arc, etc. in loading and dumping work.
However, the above-described skid steer loader has a complex mechanism and is expensive in exchange for having a desired bucket locus because it needs additional elements, such as sensors for detecting a distance slid by the slidable arm and a tilt angle of the bucket, controllers for controlling the lift arm on the basis of detection values, and several control valves.
In view of the above-described problems, the present invention aims for providing a skid steer loader which secures a wide rear and side view field for an operator in an operation control portion, and which keeps stable balance even when a lift arm is lifted up at an uppermost position. The present invention also aims for providing a simple mechanism for lifting up the lift arm keeping an opening of a bucket face almost upward.


According to the present invention, the method of heat transfer in a direction, which is reverse to natural convection, includes introduction of an additional pumping substance into the heated area. The pumping substance is incapable to be dissolved in the heat-transfer agent and its boiling temperature is lower than the boiling temperature of the heat-transfer agent. The heat-transfer agent is heated up, the pumping substance evaporates and the vapor pressure of the pumping substance is used to force the hot heat-transfer agent to flow along the branches of the circulating loop. The device for heat transfer in a direction reverse to the natural convection characterized in that its design incorporates technical means intended for vapor condensation of the pumping substance as well as technical means intended for draining that condensate from the condensation area to the evaporation area.

The present invention concerns a method and device for self-acting heat transfer in a direction reverse to natural convection. Both the method and the device can be used in various sectors of the economy for heating facilities situated below the sources of heat, e.g. for the transfer of heat from solar collectors to a tank situated below, for warming liquefied petroleum gases (propane-butane) in underground gas storage at a time of high output, to heat the ground under highways, airport runways and driveways to garages, in greenhouses or hotbeds and for transfer of waste heat recovered from chimney gases, etc.

Method and device for self-acting heat transfer in a direction reverse to natural convection

Uniwersytet Warminsko—Mazurski w Olsztynie


A battery pack includes a laminate battery having a built-in electrode held inside thereof by connecting a first sheathing film and a second sheathing film at lap sections thereof along outer peripheries of the electrode. A terminal substrate is disposed at the lap section and includes output terminals at a front surface side thereof. A substrate holder is disposed between a rear surface of the terminal substrate and the lap section, and a first metal plate is laminated on a first sheathing film side of the laminate battery. In the battery pack, the terminal substrate is supported by the substrate holder, the lap section, and the first metal plate, and the output terminals of the terminal substrate are disposed at positions so as to be brought closer to the same plane as a front surface of the second sheathing film.

The present invention relates to a battery pack including a polymer battery.
A polymer battery is manufactured by laminating sheathing films on both surfaces of an electrode and airtightly connecting the sheathing films at a circumference of the electrode. The polymer battery with this structure has an advantageous feature in that the polymer battery can be made thinner and bigger as compared to a battery in which an electrode is inserted in a metal sheathing case. However, the polymer battery has a drawback due to the lack of the metal sheathing case. Namely, since the strength of the sheathing film is weaker than the metal case, a front surface of the polymer battery is more likely to be damaged. In order to solve this adverse effect, there has been developed a battery pack in which a polymer battery is encased in a sheathing case as disclosed in Japanese Unexamined Patent Publication (KOKAI) No. 11-111250, the content of which is incorporated hereinto by reference. In the battery pack disclosed in this publication, as shown in FIG. 1 and FIG. 2, a polymer battery 21 is stored in upper and lower cases 22. The upper and lower cases 22 are manufactured by inserting metal plates 24 into plastic frames 23.
In the battery pack with the aforementioned structure, although both surfaces of the polymer battery can be protected by the metal plates, there is a drawback in that the overall battery pack becomes thick. Since it is important that the polymer battery can be made thin, if the overall thickness is increased, there is the drawback of losing the valuable and excellent advantageous feature thereof. Namely, among thin batteries manufactured by inserting electrodes into metal sheathing cases, for example, lithium ion rechargeable batteries or the like, there has been developed a thin battery having a thickness of only 3.8 mm. In view of the foregoing, it is especially important for the battery pack with the polymer battery to be made as thin as possible.
Further, it is also important for the battery pack with the polymer battery to provide solid output terminals while being made thin as a whole. When the battery pack is mounted on an electrical device, terminals of the electrical device side are elastically pressed against the output terminals, so that a solid structure is required so as not to be deformed. Since the polymer battery has the structure in which lap sections of the sheathing films are bonded at the periphery of the electrode, it is difficult to securely hold the output terminals. Especially, it is difficult to solidly hold the output terminals while the battery pack is made thin. This is because the strength of the lap section is not made sufficient if the output terminals are disposed at the lap section in order to make the battery pack thinner.
The present invention has been developed in order to solve the aforementioned drawbacks. An important object of the present invention is to provide a battery pack including a polymer battery, in which output terminals can be securely supported while the overall battery pack is made thin, and the strengths of both surfaces of the battery pack can be improved.
The above and further objects and features of the invention will more fully be apparent from the following detailed description with accompanying drawings.


Preparations of solids comprising

The invention relates to preparations of solids containing graft copolymers, to their preparation, and to formulations comprising them and to their use for pigmenting natural and synthetic materials.
Aqueous and non-aqueous coating compositions (emulsion paints, other paints), for example aqueous coating materials for fabric and paper, paper pulp, building materials, especially concrete, plasters, mortar and asphalt, natural and synthetic polymers, and aqueous and non-aqueous inks, especially inkjet inks, are nowadays pigmented using particulate solids, especially organic and inorganic pigments, together with dispersants, in the form of preparations. The function of the dispersants is the physical stabilization of the fine-particled solids (primary particles) in the preparation and/or in the application medium against reaggregation, reagglomeration or flocculation. They further serve for disaggregation and stabilization of the powder pigments or solids, which are generally in the form of aggregates or agglomerates, while the preparations are being prepared, and in particular in connection with the synthesis of organic colour pigments, as auxiliaries for controlling the morphology, crystallization and surface properties.
The dispersants used are generally nonionic, anionic, cationic or amphoteric compounds having molar masses of in general from 500 to 500,000 g/mol. In many cases, ionic dispersants are polyelectrolytes, which are usually used for aqueous applications and which stabilize the fine-particled solids by electrostatic repulsion alone or in conjunction with steric stabilization. Nonionic dispersants stabilize the particles by means of steric effects and are characterized by groups with affinity for the pigment and groups which have affinity or are soluble in the dispersion medium or application medium, e.g. binder. Electrostatic, hydrophobic and hydrogen-bond forces are primarily responsible for the interaction between dispersants and particulate solids.
Ionic dispersants have the disadvantage that their stabilizing action is heavily dependent on the electrolyte concentration of the dispersion medium or application medium.
With many particulate solids, especially organic and inorganic pigments, hydrophobic interactions with the dispersants cannot be utilized to a sufficient extent owing to the predominantly hydrophilic nature of the particle surfaces. In addition to the resultant inadequate stabilization of the particles, the preparations often have further disadvantages, such as increased foaming in conjunction with nonionic wetting agents and/or dispersants and polyelectrolytes, excessive dispersant concentrations, poor product properties such as poor colour yield in the case of organic and inorganic colour pigments, and also incompatibilities in the application media, such as flocculation or even separation of the components.
There is therefore a need for preparations of solids, especially pigment preparations or water-insoluble dye or brightener preparations, having improved properties relative to the prior art.
Preparations of solids have now been found comprising
a) a particulate solid, especially an organic or inorganic pigment, carbon black, extender pigment or metal pigment, water-insoluble or sparingly water-soluble dye or optical brightener and
b) a water-dispersible graft copolymer built up from at least one hydrophobic, ethylenically unsaturated monomer, optionally one or more ethylenically unsaturated hydrophilic monomers, and at least one natural protective colloid or protective colloid obtained from a natural protective colloid by derivatization or thermal, enzymatic, oxidative, hydrolytic or bacteriological degradation having an average molar mass of Mn greater than 500g/mol.
Particulate Solids of Component a)
By particulate solids are meant organic or inorganic solids which are insoluble or sparingly soluble in water and organic solvents, sparing solubility in water meaning a solubility of less than 100 mg/l at 20xc2x0 C., and which have a primary particle size of less than 100 xcexcm, in particular less than 10 xcexcm. They can be polymeric, amorphous or crystalline in nature and may possess lyophilic, lyophobic or amphiphilic properties, in particular lyophilic or amphiphilic, and especially hydrophilic, properties.
For the purposes of the invention they are not subject to any restriction. Particular preference is given to organic and inorganic pigments, water-insoluble dyes and optical brighteners, carbon blacks, and also metal pigments and extender pigments.
Suitable pigments and fillers are those known from the prior art as documented, for example, by Lxc3xcckert, Pigment+Fullstoff Tabellen, 5th Edition, Laatzen, 1994.
Inorganic white pigments that may be mentioned include especially oxides, such as titanium dioxide, zinc oxide (ZnO, zinc white), zirconium oxide, carbonates such as lead white, for example, sulphates, such as lead sulphate, for example, and sulphites such as zinc sulphite, for example, and lithopones; titanium dioxide is particularly preferred.
Inorganic colour pigments that may be mentioned include those from the group of the oxides and hydroxides in the form of their inorganic single compounds or mixed phases, especially iron oxide pigments, chromium oxide pigments and mixed-phase oxide pigments with a rutile or spinel structure, and also bismuth vanadate, cadmium, cerium sulphide, chromate, ultramarine and iron blue pigments.
Examples of iron oxide pigments are Colour Index Pigment Yellow 42, Pigment Red 101, Pigment Blue 11, Pigment Brown 6, and transparent iron oxide pigments. Examples of chromium oxide pigments are Colour Index Pigment Green 17 and Pigment Green 18. Examples of mixed-phase oxide pigments are nickel titanium yellow and chromium titanium yellow, cobalt green and cobalt blue, zinc iron brown and chromium iron brown, and also iron manganese black and spinel black.
Examples of inorganic black pigments that may be mentioned include those already described above together with the inorganic colour pigments, especially iron oxide black, spinel black, and black mixed-phase oxide pigments.
Furthermore, depending on the field of use, the inorganic pigments may have been organically or inorganically aftertreated.
Extenders are, in particular, substances different from the abovementioned pigments, are primarily light in colour, and are inert with respect to the binder of component b). With particular preference, the extenders are distinguished by an optical refractive index which is lower than that of the abovementioned white pigments.
Examples of inorganic extenders that may be mentioned include carbonates, such as chalk, calcite or dolomite, silicon dioxide (quartz flour), natural or synthetic silicas, silicates, such as talc, kaolin or mica, and sulphates such as heavy spar or barium sulphate (blanc fixe).
Examples of organic extenders that may be mentioned are polymeric powders and so-called hollow spheres.
Also suitable are nanoscale pigments of non-oxide ceramics, especially those from the group of the carbides, nitrides, borides and suicides of the elements Ti, Zr, Hf, Si, Ge and Sn having an average primary particle size of from 0.1 to 50 nm.
Suitable organic pigments are, for example, those of the monoazo, disazo, laked azo, xcex2-naphthol, Napthol AS, benzimidazolone, disazo condensation, azo metal complex, azo-methine metal complex, isoindolinone and isoindoline series, and also polycyclic pigments of, for example, the phthalocyanine, quinacridone, perylene, perinone, thioindigo, anthraquinone, dioxazine, quinophthalone and diketopyrrolopyrrole series. Also suitable are laked dyes, such as Ca, Mg and Al lakes of dyes containing sulphonic acid and/or carboxylic acid groups, and also carbon blacks, which for the purposes of this specification are taken to be pigments and of which a large number are known, for example, from the 2nd Edition of the Colour Index.
Mention may be made in particular of acidic to alkaline carbon blacks obtained by the gas black or furnace black process, and also chemically surface-modified carbon blacks, examples being sulpho- or carboxyl-containing carbon blacks.
Also suitable are mixed crystallizations (solid solutions) of the abovementioned organic pigments, mixtures of organic and/or inorganic pigments, with inorganic pigments or carbon black, coated metal pigments, mica pigments or talc pigrnents, e.g. mica coated by the CVD process with iron oxide, and also mixtures of the abovementioned pigments with one another.
In one particularly preferred embodiment, component a) comprises at least one pigment of the formula (I) to (III) or tautomeric forms thereof
in which
R1, R2, R3 and R4 independently of one another represent hydrogen, alkyl, especially C1-C6-alkyl, cycloalkyl, especially C5-C8-cycloalkyl, aryl, especially optionally substituted phenyl, aralkyl, especially C6-C10-aryl-C1-C4-alkyl, such as benzyl or ethyl-phenyl, or hetaryl,
B denotes the radical of an isoindoline of the formula
xe2x80x83where the linkage with the two double bonds takes place in positions 1 and 3 of the isoindolenine, and
R5, R6, R7 and R8 independently of one another represent hydrogen, halogen, especially F, Cl and Br, C1-C6-alkyl, C1-C6-alkoxy or C6-C10-aryloxy,
A denotes the radical of a cyanomethylene of the formula
xe2x80x83in which
R9 represents an electron-withdrawing radical and
Z1 to Z10 independently of one another represent O or NR10,
xe2x80x83in which
R10 represents hydrogen or cyano.
The pigments of the formula (I) are known, for example, from DE-A-39 35 858, those of the formula (II), for example, from U.S. Pat. No. 5,177,209 and those of the formula (III), for example, from U.S. Pat. No. 74 515.
Preferred pigments of the formula (I) are symmetrical isoindoline pigments corresponding to the formula (IV)
in which
R11 denotes hydrogen, C1-C6-alkyl or phenyl.
Especially preferred pigments of the formula (I) correspond to the formula (IV) in which R11 represents hydrogen.
R9 preferably represents a radical whose Hammett substituent constant (para) is greater than 0. A corresponding list of Hammett substituent constants can be found in, for example, Sykes, Reaktionsmechanismen der organischen Chemie, 9th Edition, Weinheim, VCH Verlagsgesellschaft, 1988, or can be determined in accordance with known processes.
Preferred pigments of the formula (II) are asymmetric isoindoline pigments of the formula (V)
in which
R9 denotes CN, aminocarbonyl which is optionally substituted by C1-C6-alkyl, C5-C7-cycloalkyl, aralkyl, especially C6-C10-aryl-C1-C4-alkyl, or C6-C10-aryl, and especially CONHCH3, or denotes C1-C6-alkoxycarbonyl, C6-C10-aryl-oxycarbonyl or hetaryl, especially a radical of the formula (VI) or (VII)
xe2x80x83in which
R13 and R14 independently of one another denote hydrogen, halogen, especially Cl, Br and F, C1-C6-alkyl, C1-C6-alkoxy or C1-C6-alkoxy-carbonyl or
R13 and R14 together denote the radical of a fused-on benzene ring,
G represents O, S, NH or N(C1-C4-alkyl), and
R12 denotes hydrogen, C1-C6-alkyl or phenyl.
Especially preferred pigments of the formula (V) are those in which R9 represents CONHCH3 and R12 is as defined above, especially those in which R9 represents CONHCH3 and R12 represents hydrogen.
Preferred pigments are salts, complexes, inclusion compounds, solid solutions and intercalation compounds of the formula (III). Such pigments are known, for example, from EP-A 74 515. Suitable salts and complexes of the compounds of the formula (III) are preferably the salts and complexes of the mono-, di-, tri- and tetraanions with the metals Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, with particular preference Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn. Particular importance is attached to the nickel salts, and/or nickel complexes and to their solid solutions, intercalation compounds and inclusion compounds. Particular preference is given to an inclusion compound, intercalation compound, solid solution of a salt or of a complex of azobarbituric acid, with particular preference of the 1:1 complex of azobarbituric acid and nickel.
The included compound is preferably a cyclic or acyclic organic compound, preferably carboxamides or sulphonamides, urea or substituted ureas and also heterocycles, especially 2,4,6-triamino-1,3,5-triazine, acetoguanamine and benzo-guanamine.
Particularly preferred pigments of the formula (III) correspond to the formulae (VII) and (IX)
especially in the form of their inclusion compounds or intercalation compounds, the compound included being preferably 2,4,6-triamino-1,3,5-triazine, acetoguanamine or benzoguanamine.
Water-insoluble dyes that may be mentioned include disperse dyes or whiteners (optical brighteners); examples of disperse dyes are those of the azo, disazo, anthraquinone, coumarin, isoindolinone, quinoline and methine series.
Examples of whiteners are those from the series of the correspondingly substituted stilbene, naphthalamide, pyrazoline, heteroarylcoumarin, benzoxazole, benzofuran and pyrene derivatives.
Graft Copolymer of Component b)
The graft polymer of component b) is preferably built up from
1) 90-100% by weight of one or more ethylenically unsaturated, hydrophobic monomers
2) 0-10% by weight of one or more ethylenically unsaturated, hydrophilic monomers
3) 5-300% by weight of at least one natural protective colloid or protective colloid obtained therefrom by derivatization or thermal, enzymatic, bacterio-logical, oxidative or hydrolytic degradation, where Mn is  greater than 500 g/mol,
the sum of 1) and 2) being 100 % and the amount of 3) being based on this sum.
Suitable monomers specified under 1) are all hydrophobic ethylenically unsaturated monomers such as, for example, styrene, substituted styrenes such as xcex1-methylstyrene or vinyltoluene, acrylic or methacrylic esters of alcohols having 1-18 carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-, iso- or tert-butyl acrylate, hexyl acrylate, ethylhexyl acrylate, stearyl acrylate, and also methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-, iso- or tert-butyl methacrylate, ethylhexyl methacrylate, decyl methacrylate, stearyl methacrylate, etc. Further examples are monomers such as acrylonitrile, methacrylonitrile, butadiene, isoprene, vinyl chloride, vinyl acetate or vinyl propionate.
Suitable hydrophilic monomers specified under 2) are ethylenically unsaturated compounds such as, for example, acrylic acid, methacrylic acid, acrylamide, meth-acrylamide, maleic acid, maleic anhydride, itaconic acid, N-methylolacrylamide, N-methylolmethacrylamide, styrenesulphonic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, etc. Also suitable are (meth)acrylic acid derivatives and (meth)acrylamide derivatives containing a covalently bonded dialkylamino group. Further suitable compounds are the quatemization products of these (meth)acrylic acid derivatives and (meth)acrylamide derivatives. Examples thereof are dimethylaminoethyl methacrylate, dimethylaminopropylacrylamide, trimethyl-ammonium-propylmethacrylamide chloride, etc. Ethoxylated (meth)acrylates, furthermore, are suitable.
Suitable protective colloids specified under 3) are preferably polyhydroxy compounds such as, for example, starch and starch derivatives, oxidatively, acidically, thermally, bacteriologically or enzymatically degraded starch, cellulose and cellulose derivatives, gelatin, xanthan, hydroxypropylcellulose, carboxymethylcellulose, alginic acid, casein or pectin.
Preference is given to protective colloids having ionic groups, such as anionic or cationic starches, since in that case it is possible for an ionic interaction with the pigment surface to develop. Anionic starch modified with carboxyl groups can be prepared in a simple manner by oxidatively degrading natural starch using sodium hypochlorite; cationic starch is normally prepared by derivatization with 2,3-epoxypropyltrimethyl-ammonium chloride. Phosphate starch or carboxymethyl-cellulose can likewise be used as protective colloids having anionic groups.
As the protective colloid, particular preference is given to the use of starch degraded oxidatively using hypochlorite.
The graft copolymer described under b) is preferably obtainable by polymerizing at least one ethylenically unsaturated hydrophobic monomer and optionally one or more ethylenically unsaturated hydrophilic monomers in emulsion in the presence of at least one natural protective colloid or protective colloid obtained therefrom by derivatization or thermal, enzymatic, bacteriological, oxidative or hydrolytic degradation and having a molar weight Mn of  greater than 500 g/mol.
The invention further relates to a process for preparing the preparation of the invention comprising a) and b), which is characterized either in that the two components a) and b) are mixed in water and the mixture of a) and b) is optionally separated off or in that the structural components of b) are emulsion-polymerized in the presence of component a) and the mixture of a) and b) thus prepared is optionally isolated.
The preparation of polymers in the presence of a pigment and of a protective colloid and/or emulsifier is in fact known from EP-A 104 498. It describes, however, the encapsulation of the pigment particles by polymerization of the hydrophobic monomers, the protective colloid and/or emulsifier being used to stabilize the pigments but not serving as a graft base. A nonylphenyl ethoxylate is typically used as the emulsifier. In that case, furthermore, at least a portion of the monomer amount is introduced initially, before the polymerization is initiated, in order to effect the adsorption of the monomers on the particulate solids and hence to achieve maximum encapsulation. In the case of the invention this is unnecessary: the polymer dispersion containing component b) either can be prepared, preferably, in the absence of component a), or component b) is synthesized by the feed technique in the presence of component a), particulate solids and protective colloid being introduced initially in aqueous suspension and the monomers and the free-radical initiator being metered in in parallel.
The patent DE 4 221 381 discloses graft polymers for the purpose of pigment dispersion which are prepared by free-radical graft polymerization of sugars and a mixture of monoethylenically unsaturated monomers containing carboxylic acid groups and containing sulphonic acid groups. This gives strongly anionic and water-soluble graft polymers as dispersants. The graft polymers of the invention, on the other hand, are not soluble in water but are present in the form of sterically stabilized latex particles in water.
EP-A 722 994, furthermore, describes pigmented ink preparations containing graft polymer which are characterized in that the graft polymers contain polyacrylic acid as the graft base onto which hydrophobic side chains have been grafted.
Finally, EP-A 826 751 describes aqueous preparations containing particulate solids and amphiphilic graft polymers as dispersants, both the hydrophobic part and the hydrophilic part of the graft polymer being prepared from ethylenically unsaturated monomers. In the case of the present invention only the hydrophobic graft base is prepared by polymerizing ethylenically unsaturated monomers, whereas the protective colloid c) is already present in oligomeric or polymeric form and constitutes a natural substance or has been obtained from such a substance.
The free-radically initiated polymerization can be conducted discontinuously in a batch technique, semicontinuously in a feed technique, or else continuously in a cascade of stirred vessels or in a flow pipe. In the case of the invention, preference is given to the feed technique.
The polymerization is preferably conducted with substantial exclusion of oxygen. An inert gas atmosphere of nitrogen, for example, is suitable for this purpose.
For the implementation of the batch or feed technique, a stirred vessel is appropriate. In that case it should preferably be ensured that throughout the polymerization there is thorough mixing of the reaction batch with the aid of an appropriate stirrer.
The polymerization is normally conducted at temperatures of 30-100xc2x0 C., preferably at 70-95xc2x0 C. Reaction temperatures of more than 100xc2x0 C. may likewise be employed if reaction is carried out under superatmospheric pressure in a pressure reactor.
The reaction times are preferably between 0.5 and 20 hours, more preferably between 0.75 and 5 hours.
In the case of the batch technique, the particulate solids, the protective colloid, the monomers and the free-radical initiator are preferably introduced initially in the aqueous phase and thoroughly mixed. Emulsifiers as well can optionally be added in order to increase the dispersing effect. The polymerization is started by heating the reaction mixture to an appropriate temperature, as a result of which the rate of decomposition of the respective initiator generally becomes so great that the polymerization remains ongoing. The temperature is normally held at this level until conversion of the monomers is virtually complete.
In the case of the feed technique, the free-radical initiator and the monomersxe2x80x94individually or as a mixturexe2x80x94are preferably metered at a uniform rate into the aqueous suspension containing the particulate solids and the protective colloid. Also possible is the staggered or non-uniform addition of the individual components to be added. Again, emulsifiers can optionally be added in order to increase the dispersing effect.
Examples of suitable emulsifiers are anionic or nonionic emulsifiers of low molecular mass such as sodium alkyl sulphates and sodium alkylsulphonates, sodium alkylbenzenesulphonates, sulphosuccinic esters, fatty alcohol polyglycol ethers, alkylaryl polyglycol ethers, etc. Also suitable are polymeric anionic emulsifiers based on maleic anhydride copolymers or based on oligourethanes, as are described, for example, in the European patent applications EP-A 331 066 and EP-A 400 410.
Suitable initiators are grafting-active water-soluble redox systems. Less suitable are water-insoluble initiators or sparingly water-soluble initiators based on organic peroxides or organic azo compounds.
Water-soluble redox systems which can be used are, for example, conventional initiators such as potassium peroxodisulphate, ammonium peroxodisulphate or hydrogen peroxide in combination with reducing agents such as sodium sulphite, sodium bisulphite, sodium dithionite, ascorbic acid or sodium hydroxymethane-sulphinate. Further suitable redox systems are those of hydrogen peroxide and heavy metal salts, as are described, for example, in Houben-Weyl: Methoden der Organischen Chemie, 4th Edition, Volume E 20, p. 2168. Examples of suitable heavy metals are cerium, iron and manganese. Preference is given to these redox systems containing metal ions, particular preference to the redox system composed of hydrogen peroxide and an iron(II) salt such as iron(II) sulphate or iron ammonium sulphate.
The use of the hydrogen peroxide/heavy metal salt combination ensures particularly effective grafting of the vinyl monomers onto the protective colloid. The graft yield is that portion of the polymer which is attached chemically to the protective colloid at the end of polymerization. In order to avoid a premature redox reaction, the heavy metal salt and the hydrogen peroxide are added separately. The heavy metal salt is usually added to the batch before the beginning of polymerization, while the hydrogen peroxide, in the case of the preferred feed technique, is metered in in parallel with the monomers. Owing to its catalytic action, the heavy metal salt can be used in very small amounts: concentrations of 10-300 mg of metal cation/kg are normal, although the use of higher or lower amounts is not ruled out. Hydrogen peroxide (calculated as 100% product) is used preferably in concentrations of 0.2-5.0% by weight (based on the overall amount of monomers).
Also possible is the concomitant use of the first-mentioned free-radical initiator, the addition of a reducing agent offering advantages in particular when the heavy metal salt/hydrogen peroxide system is used. The reducing agent can either be metered in in parallel to monomer mixture and hydrogen peroxide or can be introduced initially together with the heavy metal salt.
A further option is the concomitant use of chain transfer agents or regulators, which generally reduces the average molecular weight of the polymer chains grafted on. Examples of suitable chain transfer agents are ethyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, etc.
When using the initiator system comprising hydrogen peroxide and heavy metal salt, the polymerization normally comes to a standstill at monomer conversions of 95-98%. However, it is possible to reduce substantially this relatively high residual monomer content by adding a lipophilic free-radical initiator of sparing solubility in water. Suitable for this purpose are common organic peroxides such as tert-butyl hydroperoxide, di-tert-butyl peroxide, dibenzoyl peroxide or cumene hydroperoxide.
In order to obtain suspensions having a low residual monomer content, polymerization is carried out first using the redox system comprising heavy metal cation and hydrogen peroxide and, after all of the hydrogen peroxide has decomposed, an organic peroxide of sparing solubility in water, for example, is added. The organic peroxides of sparing solubility in water are characterized in that their solubility in water at room temperature is less than 1%.
The polymerization is conducted at a pH of 2-9, preferably within the weakly acidic range at a pH of 2.5-6. The pH can be adjusted to the desired level before or during the polymerization using customary acids and bases, respectively, such as hydrochloric acid, sulphuric acid, acetic acid, sodium hydroxide solution, potassium hydroxide solution, ammonia, etc. Also possible is adjustment with common acids or bases, respectively, after the end of the polymerization.
The preparations of solids of the invention, comprising components a) and b), are outstandingly suitable for dispersing and pigmenting in a large number of aqueous and non-aqueous dispersion media and application media. In particular they are suitable for pigmenting hydrophobic media and in comparison to the solids of component a) alone possess increased stability in non-polar organic media and, in conjunction with any dispersants used, in polar organic and aqueous media.
The invention additionally provides formulations further comprising in addition to components a) and b)
c) at least one dispersant and
d) optionally an aqueous and/or organic medium.
Dispersants of Component c)
The dispersants of component c) to be used in the formulations of the invention comprising the preparations of solids containing component a) and b) can be nonionic, anionic, cationic or amphoteric surface-active compounds.
For the purposes of the invention they are not subject in principle to any restriction. Depending on the use of the preparations of solids and their formulations, suitable compounds c) are available to the person skilled in the art and can be found; for example, in xe2x80x9cSurfactants Europaxe2x80x9d 3rd Edition, edited by Gordon L. Hollis, 1995.
Generally, in formations containing water as additional component d) or in formulations used in aqueous or aqueous-organic medium, both ionic and nonionic dispersants are used which possess at least one anchor group having a high adsorption capacity and affinity for the preparations of solids, and alternatively ionic groups for electrostatic stabilization, hydrophilic or water-soluble groups for steric stabilization, or both, such as polyfunctional dispersants, for example.
The dispersants possess, in particular, molecules having a molar mass of  greater than 500 to 500,000 g/mol, especially  greater than 1000 to 100,000 g/mol.
Preferred dispersants of component c) are compounds from the group of the phenol/styrene polyglycol ethers and/or ionically modified polyglycol ethers.
Preferred phenol/styrene polyglycol ethers and ionically modified polyglycol ethers have an HLB of from 10 to 20, in particular from 12 to 18.
Preferred alkoxylation products of styrene-phenol condensates are those of the formula (X)
in which
R15 denotes hydrogen or C1-C4-alkyl,
R16 represents hydrogen or CH3,
R17 denotes hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or phenyl,
m denotes a number from 1 to 4,
n denotes a number from 6 to 120,
R18 is identical or different for each unit indicated by n and represents hydrogen, CH3 or phenyl, R18 representing CH3 in from 0 to 60% of the overall value of n when CH3 is present in the various xe2x80x94(xe2x80x94CH2xe2x80x94CH(R18)xe2x80x94Oxe2x80x94)xe2x80x94 groups and R18 representing hydrogen in from 100 to 40% of the overall value of n, and R18 representing phenyl in from 0 to 40% of the overall value of n where phenyl is present in the various xe2x80x94(xe2x80x94CH2xe2x80x94CH(R18)xe2x80x94Oxe2x80x94)xe2x80x94 groups and R18 representing hydrogen in from 100 to 60% of the overall value of n.
Preferred ionically modified alkoxylation products (X) are those of the formula (XI)
in which
R15xe2x80x2, R16xe2x80x2, R17xe2x80x2, R18xe2x80x2, mxe2x80x2 and nxe2x80x2 adopt the scope of definition of R15, R16, R17, R18, m and n, respectively but independently therefrom,
X denotes the group xe2x80x94SO3xcex8, xe2x80x94SO2xcex8, xe2x80x94PO3xcex8xcex8 or xe2x80x94COxe2x80x94(R19)xe2x80x94COOxcex8,
Kat is a cation from the group H⊕, Li⊕, Na⊕, K⊕, NH4⊕ or xe2x80x94HOxe2x80x94CH2CH2xe2x80x94NH4⊕, and if X=xe2x80x94PO3xcex8xcex8 there are two Kat cations, and
R19 represents a divalent aliphatic or aromatic radical, preferably C1-C4-alkylene, especially ethylene, C2-C4 monounsaturated radicals, especially acetylene, or optionally substituted phenylene, especially ortho-phenylene, possible substituents being preferably C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or phenyl.
Particular preference is also given to mixtures of these condensates of the formulae (X) and (XI).
A further dispersant of component c) that may be mentioned is a dispersant of component c1), a condensation product based on
A) sulphonated aromatics,
B) aldehydes and/or ketones and optionally
C) one or more compounds selected from the group of unsulphonated aromatics, urea and urea derivatives.
xe2x80x9cBased onxe2x80x9d means that the condensation product may have been prepared from further reactants in addition to A, B and optionally C. Preferably, however, for the purposes of this specification the condensation products are prepared only from A, B and optionally C.
For the purposes of this specification, sulphonated aromatics of component a) include sulphomethylated aromatics. Preferred sulphonated aromatics are the following: naphthalenesulphonic acids, phenolsulphonic acids, dihydroxybenzenesulphonic acids, sulphonated ditolyl ethers, sulphomethylated 4,4xe2x80x2-dihydroxydiphenyl sulphone, sulphonated diphenylmethane, sulphonated biphenyl, sulphonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulphonated terphenyl or benzenesulphonic acids.
Particularly suitable aldehydes and/or ketones of component B) are aliphatic, cycloaliphatic and aromatic representatives. Preference is given to aliphatic aldehydes, particular preference being given to formaldehyde and to other aliphatic aldehydes having 3 to 5 carbon atoms.
Examples of suitable unsulphonated aromatics of component C) are phenol, cresol, 4,4xe2x80x2-dihydroxydiphenyl sulphone or dihydroxydiphenylmethane.
Examples that may be mentioned of urea derivatives include dimethylolurea, melamine and guanidine.
A preferred condensation product of component c1) is one based on
A) at least one sulphonated aromatic selected from the group of naphthalene-sulphonic acids, phenolsulphonic acids, dihydroxybenzenesulphonic acids, sulphonated ditolyl ethers, sulphomethylated 4,4xe2x80x2-dihydroxydiphenyl sulphone, sulphonated diphenylmethane, sulphonated biphenyl, sulphonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulphonated terphenyl and benzenesulphonic acids,
B) formaldehyde and optionally
C) one or more compounds selected from the group of phenol, cresol, 4,4xe2x80x2-dihydroxydiphenyl sulphone, dihydroxydiphenyl methane, urea, dimethylolurea, melamine and guanidine.
The condensation product obtained preferably in the condensation preferably possesses an average degree of condensation of from 1 to 150, with particular preference from 1 to 20, in particular from 1 to 5.
The condensation products of component c1) can be used in the form of an aqueous solution or suspension or as a solid, for example as powder or granules, preferably as spray-dried powder or granules.
Preferred condensation products of component c1) have an inorganic salt content of less than 10% by weight, preferably less than 5% by weight, in particular less than 1% by weight, based on the aqueous solution or suspension of the component that is used or based on the solid of component c1) that is used.
It is likewise preferred to use condensation products of the component c1) that are low in residual monomer or free from residual monomer.
xe2x80x9cLow in monomerxe2x80x9d refers to a residual monomer content of less than 30% by weight, preferably less than 20% by weight, based on the condensation product, in particular  less than 10% by weight, preferably  less than 5% by weight. Residual monomers in this context are the reactants used to prepare the condensation product.
Low-salt condensation products of this kind which are low in residual monomer are known, for example, from EP-A 816 406.
The condensation products of components c1) can be prepared, for example, by first preparing the sulphonated aromatics of component A) optionally in a mixture with unsulphonated aromatics of component C) by reacting the parent aromatics with a sulphonating agent, preferably sulphuric acid, especially concentrated sulphuric acid, chlorosulphonic acid, amidosulphonic acid or oleum.
It is preferred to use from 0.4 to 3.2 mol, in particular from 0.8 to 1.6 mol, of sulphonating agent per mole of the aromatic on which component A) is based.
This is followed by the condensation with aldehydes and/or ketones of component B), preferably formaldehyde, optionally together with further compounds of component C). The condensation takes place preferably in aqueous solution at a pH of from 0 to 9. In this case it is preferred to use from 0.4 to 1.5 mol, in particular from 0.4 to 1.0 mol, of component B) per mole of the sulphonated aromatic A) or per mole of a mixture of sulphonated aromatics of component A) and unsulphonated aromatics of component C).
This is followed optionally by the neutralization of the sulphonate condensation product of component c1) with a base.
The separation of the inorganic acid or its salts and the reduction in the residual monomer content can be implementing using, for example, membrane separation techniques. Preferred membrane separation techniques in this context are ultrafiltration, diffusion dialysis or electrodialysis.
The membranes used in the membrane separation techniques, preferably in the ultrafiltration, in one preferred embodiment possess a molecular weight cutoff (MWCO) of from 1000 to 10,000 daltons.
The separation of the inorganic acid with the aid of a membrane separation technique takes place preferably by the method of diafiltration with acid-stable ultrafiltration or nanofiltration membranes in cross-flow filtration mode. Examples of suitable membranes in this case are polyhydantoin membranes, as known from EP-A 652 044.
Preferred membranes for this purpose possess an MWCO level of from 2000 to 10,000 daltons. Optionally, concentration takes place simultaneously with this process step.
A further dispersant is a dispersant of component c2)
c2) being a compound from the group of phosphoric acid, phosphonic acid and/or derivatives thereof.
Compounds of group c2) embrace phosphoric acid derivatives, phosphonic acid derivatives such as, for example, the reaction products of phosphoric acid or phosphonic acid with polyols and/or monoalcohols.
Phosphoric acid derivatives are preferably phosphoric monoesters and diesters of the general formula
where
R4 and R5 independently denote an organic radical having 1-20 carbon atoms and
X⊕ represents H, or a monovalent cation.
Preferred compounds of the formula (XIII) or (XIV) are the alkali metal salts of phosphoric diesters having C6-C10 aliphatic radicals, especially sodium dioctyl phosphate.
Phosphonic acid derivatives are preferably compounds of the general formula
in which
R6 represents H, or an organic radical having 1-20 carbon atoms,
R7 denotes C11-C22-alkyl or cycloalkyl, C7-C18-aralkyl, or a radical of the general formula
xe2x80x94R9xe2x80x94Oxe2x80x94COxe2x80x94R10
xe2x80x83or
xe2x80x94R9xe2x80x94COOxe2x80x94R10,
xe2x80x83where
R9 denotes an optionally substituted C2-C4-alkylene radical, and
R10 denotes a C6-C22-alkyl, cycloalkyl or alkylene radical;
in particular, R7 may be a radical of C4-C7-dicarboxylic or tricarboxylic acid or derivatives thereof (e.g. esters), for example the radical of butane-1,2,4-tricarboxylic acid, ethanedicarboxylic acid or derivatives thereof. (Compounds of this kind of the formula (XV) can be obtained, for example, by subjecting phosphites to addition reaction with unsaturated dicarboxylic or tricarboxylic acid (or derivatives thereof).)
R8 represents H or CH3.
Preferred compounds are phosphonosuccinic acid or phosphono-1,2,4-tricarboxylic acid.
The derivatives can be used in particular in the form in which they are neutralized with monofunctional bases.
Reaction products of the said compounds are obtained by reacting phosphonic acid derivatives, examples being their esters based on low-boiling alcohols, with polyols and/or alcohols. Suitable polyols are polyethylene glycols and/or polypropylene glycols having 2-50 molar units, especially 5-20 molar units, of alkylene oxide.
Suitable alcohols are straight-chain, branched or cycloaliphatic C6-C22 alcohols or mixtures thereof, preferably fatty alcohols.
With particular preference, the reaction products correspond to the general formula
where
R6, R8 are as defined above,
R11 is C6-C22-alcohol, preferably aliphatic or cycloaliphatic alcohols, especially fatty alcohols,
n is 1-10,
R12 is H, CH3,
R13 is H, CH3.
The reaction products can optionally be used in the form in which they are neutralized with monofunctional bases.
The pigment preparations of the invention may comprise as additional dispersants of component c) those, for example, which are specified below.
c3) Oxalkylation products obtainable by condensing aromatics containing phenolic OH groups with formaldehyde and NH-functional groups, examples being those from the group of the novolaks or alkylaryl polyglycol ethers.
Preference is given to oxalkylation products of this kind obtainable by condensing aromatics having phenolic OH groups with formaldehyde and amines containing a formaldehyde-reactive NH group, or derivatives of such oxalkylation products. Preference is given to those obtained by oxalkylating compounds of the formula (XVI)
in which
R1 denotes the monovalent radical of an optionally substituted aliphatic, cycloaliphatic or aromatic hydrocarbon,
R2 denotes hydrogen or the monovalent radical of an optionally substituted aliphatic, cycloaliphatic or aromatic hydrocarbon and
R3 denotes hydrogen, C1-C20-alkyl, C5-C7-cycloalkyl, phenyl, benzyl, halogen, hydroxyl, C1-C18-alkoxy, carboxyl or C1-C18-alkoxycarbonyl,
the oxalkylation reagents used being preferably ethylene oxide, propylene oxide, butylene oxide, styrene oxide, glycide or mixtures of these compounds, but especially ethylene oxide, optionally together with propylene oxide. Oxalkylation products of this kind are described, for example, in DE 27 11 240.
c4) Water-soluble polyisocyanate adducts containing hydrophilic polyether chains containing preferably not more than 1.0% by weight of isocyanate groups, 30-99.5% by weight of ethylene oxide units arranged within polyether chains and incorporated by way of monofunctional alcohols, and having an ionic group content of 0-200 milliequivalents/100 g of polyisocyanate adduct.
Dispersants of this kind are disclosed, for example, in DE-A 1 963 382.
Preferred polyisocyanate adducts of component c4) are prepared, for example, while observing an NCO index of from 100 to 130, by reacting
A) a polyisocyanate component having an average NCO functionality of from 3.0 to 6 and an NCO content of from 7 to 30% by weight, consisting of isocyanurate-group-containing modification products of 2,4-diisocyanatotoluene or its mixtures with up to 35% by weight, based on the mixture, of 2,4-diisocyanatotoluene, with
B) from 50 to 90 equivalent-%, based on component A), of a monovalent alcohol component consisting of at least one monovalent polyether alcohol from the molecular weight range from 150 to 10,000, preferably from 150 to 5000 g/mol, having an ethylene oxide unit content of from 40 to 99.5% by weight, and prepared by alkoxylating a monovalent starter molecule,
C) from 0 to 20 equivalent-%, based on the isocyanate groups of A), of a monovalent compound containing isocyanate-reactive groups, from the molecular weight range from 32 to 5000 g/mol, which additionally contains ionic groups, and
D) from 10 to 50 equivalent-%, based on component A), of an amine component consisting of at least one tertiary amine from the molecular weight range from 88 to 250 g/mol having a group which is reactive towards isocyanate groups in the sense of the NCO addition reaction,
with urethane formation and optionally secondary reactions, carried out simultaneously with or subsequent to the urethane formation, to reduce the level of any excess NCO groups present to a residual content of not more than 1.0% by weight, the nature and proportions of the starting components being chosen such that the reaction product contains from 40 to 75% by weight of ethylene oxide units incorporated by way of component B).
Likewise preferred polyisocyanate adducts of component c4) are prepared, for example, while observing an NCO index of from 131 to 600, by reacting
A) a polyisocyanate component having an average NCO functionality of from 1.7 to 2.5 and an NCO content of from 30 to 65% by weight, consisting of at least one isocyanate from the following group: 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4xe2x80x2-diisocyanato-diphenylmethane, 2,4xe2x80x2-diisocyanato-diphenylmethane, with
B) from 5 to 50 equivalent-%, based on component A), of an alcohol component consisting of the type specified above under B),
C) from 0 to 10 equivalent-%, based on the isocyanate groups of A), of a monovalent compound containing isocyanate-reactive groups, from the molecular weight range from 32 to 5000 g/mol, which additionally contains ionic groups, and
D) from 0 to 20 equivalent-%, based on component A), of an amine component of the type specified above under D),
with urethane formation and optionally secondary reactions, carried out simultaneously with or subsequent to the urethane formation, to reduce the level of any excess NCO groups present to a residual content of not more than 1.0% by weight, the nature and proportions of the starting components being chosen such that the reaction product contains from 40 to 75% by weight of ethylene oxide units incorporated by way of component B).
With particular preference, the abovementioned pigment preparations of the invention contain as dispersant of component c4) a polyisocyanate adduct containing from 10 to 50 milliequivalents of ionic groups per 100 g of component c4).
c5) Water-soluble inorganic salts, especially borates, carbonates, silicates, sulphates, sulphites, selenates, chlorides, fluorides, phosphates, nitrates and aluminates of the alkali metals and alkaline earth metals and of other metals, and also ammonium;
Compounds from the group of the water-soluble salts are used preferably for preparing the preparations of the invention based on inorganic pigments or extenders (component a).
Compounds of this group are generally used together with another of the abovementioned compounds of component c). The amount of the compounds of the group mentioned, based on pigment, is from 0.01 to 10% by weight, preferably from 0.2 to 4% by weight.
Particular preference is given to magnesium sulphate.
c6) Polymers composed of repeating succinyl units, especially polyaspartic acid
In one preferred embodiment the polymers of component c6) have repeating succinyl units comprising one of the following structures:
preferably
which structures may optionally be present in salt form as well.
By xcex1- and xcex2-form is meant in each case the peptide linkages obtained as a result of the carboxyl groups in xcex1 or xcex2 position, respectively.
In addition, further repeating units may be present as a result of appropriate reaction regime and choice of starting materials, examples of these units being
a) malic acid units of the formula
b) maleic and fumaric acid units of the formula
c) iminodisuccinate units of the formula
The chemical structure is analyzed preferably by 13C-NMR, FT-IR and, following total hydrolysis, by HPLC, GC and GC/MS.
Many production processes initially produce not the pure acids but rather the corresponding anhydrides, an example being polysuccinimide (PSI). Polymerization products of this kind can be converted to a salt by reaction with a base, optionally in the presence of water. This conversion takes place subsequently in an appropriate apparatus by means of hydrolysis. Preference is given here to a pH of between 5 and 14. In a particularly preferred form a pH of from 7 to 12 is chosen, achieved in particular through the addition of a base. Suitable bases are alkali metal hydroxides and alkaline earth metal hydroxides or carbonates such as, for example, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate or potassium carbonate, ammonia and amines such as triethylamine, triethanolamine, diethylamine, diethanolamine, alkylamines, etc.
In addition to free acids, particular preference is given to their Na, K or Ca salts.
The temperature during hydrolysis is suitably within a range up to and including the boiling point of the PSI suspension and is preferably from 20 to 150xc2x0 C. The hydrolysis is optionally carried out under pressure.
It is, however, also possible to obtain the free acid, especially polyaspartic acid, by purely aqueous hydrolysis or by treatment of the salt with acids or with acidic ion exchangers. For the purposes of the present invention, the term xe2x80x9cpolyaspartic acidxe2x80x9d (=PAS) likewise includes the salts, unless expressly stated otherwise.
The polymers of component c6) can be used in the form of an aqueous solution or suspension, or as a solid, and as powder or granules, preferably as spray-dried powder or granules.
Preferred polymers have a molecular weight, according to analyses by gel permeation chromatography, of Mw=500 to 10,000, preferably 70 to 5000, with particular preference 1000 to 4500. In general, the proportion of the beta-form is more than 50%, preferably more than 70%.
The crude polymers can be freed from monomeric fractions by customary methods of working up, for example by extraction with water and 1 N hydrochloric acid, or by membrane separation techniques. Suitable membrane separation techniques were described earlier in connection with component c1).
The preparation of the polymers of component c6) having repeating succinyl units, especially of xcex1/xcex2-polyaspartic acids and polysuccinimides, is known per se; see U.S. Pat. No. 4,839,461 (=EP-A 0 256 366).
Moreover, further additional dispersants of group c7) can be used in the pigment preparations of the invention and are advantageous for the dispersion of the pigments in the course of the preparation processes.
These dispersants can be nonionic, anionic, cationic or amphoteric compounds. Examples of nonionic dispersants of c7) are the following: alkoxylates, alkylolamides, esters, amine oxides and alkyl polyglycosides.
Further suitable nonionic dispersants are the following: reaction products of alkylene oxides with alkylatable compounds, such as fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, carboxamides and resin acids, for example. These dispersants are, for example, ethylene oxide adducts from the class of the reaction products of ethylene oxide with:
a) saturated and/or unsaturated fatty alcohols having 6 to 20 carbon atoms or
b) alkylphenols having 4 to 12 carbon atoms in the alkyl radical or
c) saturated and/or unsaturated fatty amines having 14 to 20 carbon atoms or
d) saturated and/or unsaturated fatty acids having 14 to 20 carbon atoms or
e) hydrogenated and/or unhydrogenated resin acids,
f) esterification products and/or arylation products prepared from natural or modified, optionally hydrogenated castor oil fatty substances, the products being optionally linked by esterification with dicarboxylic acids to form repeating structural units.
Particularly suitable ethylene oxide adducts are the alkylatable compounds specified under a) to e) with from 5 to 120, preferably from 5 to 60, in particular from 5 to 30, mol of ethylene oxide.
Examples of polymeric dispersants are the compounds listed in the index xe2x80x9cWater-Soluble Synthetic Polymers: Properties and Behaviorxe2x80x9d (Volumes I to II by Philip Molyneux, CRC Press, Florida 1983/84).
Particular preference is given to nonionic polymeric dispersants.
Examples of suitable polymeric dispersants are water-soluble and water-emulsifiable compounds having an average molecular weight of 1000-100,000 g/mol, preferably 2000-40,000 and, in particular, from 2000 to 30,000 g/mol, examples being homopolymers and copolymers, graft polymers and graft copolymers, and also random block copolymers.
Examples of particularly preferred polymeric dispersants are AB, BAB and ABC block copolymers. In the AB or BAB block copolymers, the A segment is a hydrophobic homopolymer or copolymer which ensures a connection to the pigment and the B block is a hydrophilic homopolymer or copolymer or a salt thereof and ensures the dispersing of the pigment in the aqueous medium. Polymeric dispersants of this kind and their synthesis are known, for example, from EP-A-518 225 and EP-A-556 649.
Further examples of suitable polymeric dispersants are polyethylene oxides, polypropylene oxides, polyoxymethylenes, polytrimethylene oxides, polyvinyl methyl ethers, polyethyleneimines, polyacrylic acids, polyarylamides, polymethacrylic acids, polymethacrylamides, poly-N,N-dimethyl-acrylamides, poly-N-isopropylacrylamides, poly-N-acryloylglycinamides, poly-N-methacryloylglycinamides, polyvinyloxazolidones, polyvinylmethyloxazolidones.
Examples of anionic dispersants are the following: alkyl sulphates, ether sulphates, ether carboxylates, phosphate esters, sulphosuccinate amides, paraffin sulphonates, olefin sulphonates, sarcosinates, isothionates and taurates.
Particular preference is given to anionic polymeric dispersants.
Suitable anionic polymeric dispersants are, in particular, condensation products of aromatic sulphonic acids with formaldehyde, such as condensation products of formaldehyde and alkylnaphthalenesulphonic acids or of formaldehyde, naphthalenesulphonic acids and/or benzenesulphonic acids, and condensation products of optionally substituted phenol with formaldehyde and sodium bisulphite.
Also suitable are condensation products obtainable by reacting naphthols with alkanols, subjecting the product to addition reaction with alkylene oxide, and converting at least some of the terminal hydroxyl groups into sulpho groups or monoesters of maleic acid, phthalic acid or succinic acid.
Also suitable, moreover, are dispersants from the group of the sulphosuccinic esters, and also alkylbenzenesulphonates, as are ionically modified, alkoxylated fatty acid alcohols or salts thereof. Alkoxylated fatty acid alcohols are in particular saturated or unsaturated C6-C22 fatty acid alcohols, especially stearyl alcohol, which have been provided with from 5 to 120, preferably from 5 to 60 and, in particular, from 5 to 30 ethylene oxide units. Particular preference is given to a stearyl alcohol alkoxylated with from 8 to 10 ethylene oxide units. The ionically modified alkoxylated fatty acid alcohols are preferably in salt form, especially as alkali metal salts or amine salts, preferably as the diethylamine salt. Ionic modification is, for example, sulphating, carboxylating or phosphating.
Further examples of anionic polymeric dispersants are the salts of polyacrylic acids, polyethylenesulphonic acids, polystyrenesulphonic acid, polymethacrylic acids and polyphosphoric acids.
Additional examples of anionic polymeric dispersants are copolymers of acrylic monomers, which are indicated by way of example in the following table by a combination of the following monomers and which are synthesized to random, alternating or graft copolymers:
acrylamide, acrylic acid;
acrylamide, acrylonitrile;
acrylic acid, N-acryloylglycinamide;
acrylic acid, ethyl acrylate;
acrylic acid, methyl acrylate;
acrylic acid, methylenebutyrolactam;
N-acryloylglycinamide, N-isopropylacrylamide;
methacrylamide, methacrylic acid;
methacrylic acid, benzyl methacrylate;
methacrylic acid, diphenylmethyl methacrylate;
methacrylic acid, methyl methacrylate;
methacrylic acid, styrene.
Further anionic polymeric dispersants are styrene-maleic anhydride copolymers, copolymers thereof with the abovementioned acrylic monomers, and also polyurethane-based polymers.
Also suitable are lignin-based compounds, especially lignin sulphonates, e.g. those obtained by the sulphite or kraft process. They are preferably products which in part are hydrolysed, oxidized, propoxylated, sulphonated, sulphomethylated or di-sulphonated and fractionated by known processes, for example in accordance with the molecular weight or in accordance with the degree of sulphonation. Mixtures of sulphite and kraft ligninsulphonates are also highly effective. Particularly suitable ligninsulphonates are those having an average molecular weight of more than 1000 to 100,000, an active ligninsulphonate content of at least 80% by weight and, preferably, a low polyvalent cation content. The degree of sulphonation can vary within wide limits.
Examples of cationic dispersants are as follows: quaternary alkylammonium compounds and imidazoles.
Particular preference is given to cationic polymeric dispersants.
Examples of cationic polymeric dispersants are the salts of polyethyleneimines, polyvinylamines, poly(2-vinylpyridines), poly(4-vinylpyridines), poly(diallyldimethylammonium) chloride, poly(4-vinylbenzyltrimethylammonium) salts and poly(2-vinylpiperidine).
Preferred cationic polymeric dispersants contain neutralized tertiary amino groups and/or quaternary ammonium groups. Particularly preferred compounds are described in Le A 28 798.
Examples of amphoteric dispersants are the following compounds: betaines, glycinates, propionates and imidazolines.
Anionic and cationic polymers are summarized as polyelectrolytes and are fully or partly dissociable in an aqueous and/or organic phase.
Where the formulations contain as additional component d) an organic medium or non-aqueous medium in the wider sense, or are employed in such media, suitable dispersants of component c) are primarily those which
1) possess at least partial solubility in the media
2) possess a group (so-called anchor group) having a high capacity for adsorption on the preparations of solids containing components a) and b) and optionally
3) additionally contain groups which provide steric stabilization of the preparations of solids in the media.
Generally suitable are nonionic polymeric dispersants having molecular weights of from 1000 to 500,000, such as, for example,
homopolymers and copolymers, graft polymers and graft copolymers, and also linear and random block copolymers, especially the AB, BAB and ABC block copolymers mentioned earlier above, and especially block copolymers of ethylene oxide and propylene oxide as are obtainable, for example, under the names Triton(copyright), Pluronic(copyright), Tetronic(copyright),
homopolymers and copolymers of vinyl alcohol and/or vinylpyrrolidone,
acrylamides, methacrylamides and polymers containing these compounds, the latter especially if the preparations of solids possess acidic anchor groups,
carboxylated styrene-butadiene polymers, obtainable for example from anionic polymerization of styrene, butadiene and subsequent reaction with thioglycolic acid, especially in the form of their AB-type block copolymers,
monoalkoxy titanates, obtainable for example under the name KenReact(copyright) from the company Kenrich,
random and linear block copolymers based on optionally styrene and acrylic monomers, especially as disclosed in U.S. Pat. No. 4,339,365,
polymers based on a reaction product of one or more polyisocyanates having an average functionality of  greater than 2 with at least one monohydroxy compound and optionally a compound containing at least one basic ring nitrogen and an isocyanate-reactive group, as described for example in EP 520 586.
Where component a) of the formulation of the invention comprises an organic or inorganic pigment or carbon black, preferred dispersants of components c) are
urethanized homopolymers or copolymers, with particular preference hydroxyl-containing homopolymers or copolymers of vinyl-containing comonomers with compounds containing isocyanate groups
or a
polyisocyanate addition product containing polyether chains and having an isocyanate group content of not more than 1.0% by weight and containing from 30 to 95% by weight of ethylene oxide units which are arranged within polyether chains and have been incorporated by way of monofunctional alcohols.
Based on the overall preparation, the preparations of solids of the invention contain preferably
a) 10-99.9% by weight, preferably 40-99% by weight, of at least one particulate solid of component a)
b) 0.1-90% by weight of the graft copolymer of component b), preferably from 1 to 60% by weight.
The formulations of the invention contain preferably
a+b) 0.1-99% by weight of the preparation of solids comprising components a) and b)
c) 0.1-100% by weight of at least one dispersant of component c), based on the sum of components a) and b), and
d) 0-99% by weight of water and/or organic medium.
In one preferred embodiment component a) comprises an organic or inorganic pigment, preferably carbon black or metal pigment.
When the preparations of solids or the formulations prepared from them are used in aqueous or aqueous-organic media, component a) comprises a pigment or carbon black having hydrophilic surface properties, which may optionally further contain acidic or alkaline surface groups.
By way of example, for the purposes of the invention, particulate solids may be understood as pigments, especially acidic and alkaline carbon blacks, hydrophilic inorganic pigments and organic pigments, especially those corresponding to the formulae I, II and III, but without restricting the scope of the invention.
In the text below, formulations are understood by way of example to be pigment formulations comprising the abovementioned pigments as component a).
The invention further provides a process for preparing the formulations of the invention comprising the pigment preparations consisting of components a) and b) and also the dispersant c) and optionally an aqueous and/or organic medium d).
Aqueous formulations are preferably prepared by carrying out homogeneous mixing of pigment preparations comprising components a) and b), prepared by free-radical emulsion polymerization of component b) in the presence of the pigment of component a), optionally in the form of its water-moist presscake, together with at least a portion of the dispersant of component c) and optionally water and/or organic medium of component d), and subsequently subjecting this homogeneous mixture to continuous or batchwise wet comminution.
Suitable wet comminution methods include, for example, dispersion by means of a stirrer or dissolver, grinding by means of stirred ball mills or bead mills, kneading or high-pressure homogenization.
Subsequently, the resulting dispersion is adjusted to the desired pigment formulation, optionally with further water or aqueous-organic medium and, optionally, further necessary portions of component b) and/or c).
In accordance with the invention, the optionally standardized dispersions can also be converted to the dry form by means of an appropriate process.
Suitable drying processes that may be mentioned include the following: spray drying, especially single-fluid spray drying using high-pressure nozzles or swirl chamber nozzles, plate spray drying, spray drying with integrated or downstream fluid-bed agglomeration and/or fluid-bed drying, freeze drying with upstream or downstream granulation, spray-freeze drying, buildup granulation, for example by the plate or drum granulation process, optionally with partially predried product, fluidized-bed drying and granulation, mixer agglomeration and mixer drying, optionally in combination with fluidized-bed or fluid-bed drying, mix-agglomeration in suspension with downstream fluidized-bed or fluid-bed drying, granulation by means of paste-forming with downstream afterdrying and comminution, and steam jet agglomeration.
Combinations of the processes mentioned are likewise possible.
Particular preference is given to the processes of spray drying by means of swirl chamber nozzles, spray drying with integrated or downstream fluidized-bed agglomeration and/or drying, buildup granulation by the plate process, and also fluidized-bed granulation and drying.
If desired, fractions of the other components may also be introduced directly before or during the drying and granulation process.
In accordance with the invention, the aqueous pigment formulations of the invention can also be prepared by carrying out homogeneous mixing of pigment or water-moist press cakes of component a), an aqueous suspension of component b) together with at least a portion of the dispersant of component c) and also optionally water of component d), subjecting this homogeneous mixture to wet comminution and optionally standardizing or drying it as described above.
Pigment formulations of the invention in an organic medium are prepared, for example, by carrying out homogeneous mixing of a preferably water-free pigment preparation comprising components a) and b) in an organic medium of component d), for example an organic solvent, plasticizer and/or polyether polyol or polyester polyol, or polymer together with at least a portion of the dispersant of component c) and, subsequently, optionally subjecting this mixture to dispersion to the desired state of fine division by means of an appropriate apparatus such as, for example, a dissolver, kneading apparatus, roll mill, ball mill, high-speed stirred bead mill or high-pressure homogenizer. Component c) is preferably dissolved in or mixed homogeneously into the organic medium of component d) before the pigment preparation is added.
The pigment formulations of the invention may optionally contain further additives; examples in aqueous formulations that may be mentioned are the following:
surface-active compounds such as, for example, further dispersants, emulsifiers or wetting agents, pH regulators, preservatives and stabilizers, UV stabilizers and also optionally oleophobicizing agents and/or dust-binding agents.
Besides water, particularly preferred organic media of component d) are solvents which are nonvolatile under atmospheric pressure, examples being polyether polyols in the form of their homopolymers, copolymers and block copolymers having a boiling point under atmospheric pressure of more than 150xc2x0 C., preferably more than 250xc2x0 C.
The pigment preparations of the invention are notable for very good compatibility with hydrophobic media, especially organic hydrophobic media.
For example, they are outstandingly wettable and readily dispersible in synthetic and natural polymers and relative to the prior art result in better active substance performance, for example high colour intensity and ease of dispersibility in the case of organic and inorganic colour pigments.
Additionally, the pigment preparations possess a high affinity for a large number of dispersants of component c) and are therefore easy to stabilize into the formulations of the invention in water, aqueous-organic medium or organic medium.

Preparations of solids containing graft copolymers

Abstract: Preparations of solids comprising

Abstract: a) at least one particulate solid

Abstract: and

Abstract: b) a water-dispersible graft copolymer built up from at least one hydrophobic, ethylenically unsaturated monomer, optionally one or more ethylenically unsaturated hydrophilic monomers, and at least one natural protective colloid or protective colloid obtained from a natural protective colloid by derivatization or thermal, enzymatic, oxidative, hydrolytic or bacteriological degradation having an average molar mass of Mn greater than 500 g/mol.


The invention features a substrate and compositions, kits, devices, and methods employing the substrate that produces an isolated population of cells from a general population. The isolated population is enriched for one or more target populations. Substrate is can be liquefied and allows recovery of unlabeled, viable, and functional cells.

Cell-based therapies promise to transform healthcare in the coming decades, offering breakthrough treatments for cancer, diabetes, and numerous other diseases impacting patients globally. However, to realize this potential, a method for producing functional cells in a safe and economically viable manner is needed. The enrichment of a target cell population, and subsequent cultivation of desired cells from a defined cell population, is an important first step in many complex biologic and biomedical workflows. Thus, improved cell enrichment processes will contribute to an overall simplified experimental protocol in the fields of fundamental biological research, tissue engineering, regenerative medicine, and diagnostics/therapeutic health monitoring. The production of advanced cell-based therapeutics requires purification of cells on the basis of surface antigen expression, as such cells cannot be distinguished from others in the same source (e.g. blood or tissue) via physical parameters, such as size or density, alone. Purification of such cells therefore typically requires tagging with surface markers.
Current clinical laboratory and basic biology research applications face significant challenges in the isolation and study of target cells of interest, including: (1) difficulty in achieving high purity multi-marker-based cell isolation from a complex blend of non-target cells; (2) complex native environments with extremely heterogeneous populations, such as blood cells and bone marrow; (3) inaccurate analysis of blood character and condition required for isolation of a few desired cells; (4) inefficient large-scale cell enrichment for low starting cell concentrations in cases such as stem or progenitor cells; (5) effective sorting of two or more cell types with high cell viability to support numerous biomedical pursuits.
Currently, physical separation techniques are commonly used for pre-purification and concentration but have low specificity and are difficult to process on a large scale. Magnetic separation is expensive, slow, and laborious. In cases requiring positive selection techniques, magnetic separation leaves residual magnetic beads attached to purified cells and can impede proliferation and reduce viability. These residual beads ultimately reduce cell efficacy in transplantation and engraftment applications.
There is a need for effective cell separation techniques that deliver high cell purity and yield while maintaining cell function.

Compositions, devices, and methods for cell separation