A pill assembly configured to receive the correct selection of medications in the correct dosages for a particular patient. The pill assembly comprises containers wherein at least one of the containers is configured to receive a plurality of different pills. The containers are adjacent to one another. The pill assembly also comprises a plurality of lids. Each of the lids is configured to seal a corresponding container. The containers have a top surface with a flange that is configured to receive the corresponding lid. Each lid has a surface that is configured to receive a printable indicia with patient specific information. The pill assembly may also comprise a sleeve that is configured to slidably interface with the containers.

1. Field
This description relates to the field of pill packaging and delivery systems. More particularly, this description relates to a pill assembly, an apparatus for storing pills, and a method for dispensing pills.
2. Description of Related Art
One of the major problems in the taking of prescribed daily medications emanates from the fact that, in many instances the patient has to take more than one medication in the form of tablets or pills. The concern is based on determining whether all medications have been taken in compliance with the prescribed daily regimen. Many times this concern is compounded by the requirement that portions of the various medications must be taken at different times during the day.
The fear of taking improper dosages of prescribed medication can be particularly acute in the elderly, many of whom have some degree of mental dementia and can easily be confused as to whether they have taken all of their medications at the correct time. Some patients, with curtailed mental capabilities, have difficulty just in sorting out the medications preparatory to taking them, let alone taking the medication in a timely manner. Providing medications to disabled and/or incapacitated individuals can also be a problem for care givers, particularly those in hospitals and assisted living facilities where one caregiver may oversee the medication of many patients.
Thus, there is a need for a positive delivery system and pill package assembly for the delivery of multi-prescription dosages. A pill packaging and delivery system which could decrease the possibility of human error and provide an easy to use set-up for the correct selection and delivery of multi-tablet/multi-time medications would be welcomed by the pharmaceutical and medical communities.
There is also a need for a pill delivery system that could provide evidence that the prescriptions were actually taken or administered as prescribed. Such a system would be an efficient way for any patient to take such multi-dosages but it would be especially beneficial for a patient of limited mental capacity as well as to caregivers in the hospital setting.
There is also a need for a pill assembly and delivery system for vitamin supplements. Vitamin supplements are also often used in the same manner as many prescribed drug regiments with many of the same problems and inconveniences. Therefore a delivery system that addresses the needs of multi-prescription administration also contains many benefits for, and can be applied to, the vitamin and herbal supplement market.

Pill assembly for pill packaging and delivery systems


A system and method for generating a multi-tone representation of a digital image by applying a plurality of functions of luma to the digital image. The functions of luma comprise at least a first function and a second function, where each function has a value for each luma value in a range of luma values. Each function also has an associated display value. The digital image includes a plurality of pixels, where for each pixel, it is determined which of the first and second functions has a maximum value for a luma value of the pixel. Each pixel is represented using the display value associated with the determined function.

Digital non-linear editing (DNLE) is a process by which digital media may be edited. DNLE, as the name implies, is performed on digital media stored as data in digital media files on a digital random access medium. DNLE may be conducted in a non-linear fashion because the digital media files in which the digital media is stored can be randomly accessed. Thus an editor may access a piece of the digital media without having to proceed sequentially through other pieces of the digital media stored in the same or other digital media files. More than one editor also may be able to access different pieces of the same digital media contemporaneously. The digital media may be a digitized version of a film or videotape or digital media produced through live capture onto a disk of a graphics or animation software application. Example commercial DNLE systems include the Media Composer® or the Avid® Symphony™ video production system or, NewsCutter® news editing system available from Avid Technology, Inc. For a more detailed description of DNLE, see Digital Nonlinear Editing, New Approaches to Editing Film and Video, 1993,by Thomas Ohanian.
Color modification is a class of operations that may be performed on media data. Color modification is used both to correct color errors due to process errors and to adjust the colors used in the video for artistic expression. Such color modifications may include enhancing contrasts or color in an image to give a program an overall "look," or applying special effects to selected segments. Other color modifications may be made by an editor to correct problems with color or lighting resulting from the source of the media. Such corrections may include color balancing for camera and lighting differences, correcting for film processing differences, matching colors and tones from shot to shot, or adjusting video levels for differences in source tapes, source decks, etc.
Digital images are comprised of an array of picture elements called pixels. For a given image, color modifications may be applied to all pixels in the image or pixels comprising a portion of the image. In digital video signal processing, a variety of data formats can be used to represent the color of pixels within a digital image. Formats may be classified into two major categories: composite signals and component signals. Component formats represent a color as multiple components, each component defining a value along a dimension of the color space in which the color being represented is defined. A composite video is an analog signal that uses a high frequency subcarrier to encode color information. The subcarrier is a sinewave of which the amplitude is modulated by the saturation of the color represented by the signal, and the hue of the color is encoded as a phase difference from a color burst. Analog composite signals are generally used to broadcast television video signals.
There are a variety of component formats used to represent color. RGB (Red, Green, Blue) format represents a color with a red component, a green component and a blue component. CMY (Cyan, Magenta, Yellow, Black) format represents a color with a cyan component, a magenta component, and a yellow component. CMY is a format commonly used by printers. The CMY components are color opposites of RGB components. In a three-dimensional coordinate system, each component of either the RGB or the CMY format represents a value along an axis, the combination of the values defining a cubic color space.
The data formats HSL (Hue, Saturation, Lightness or Luminance) and HSV (Hue, Saturation, Value) represent a color with a hue component, a saturation component, and a luma component. In a three-dimensional coordinate system, the luma component represents a value along a luma axis, the hue component represents the angle of a chroma vector with respect to the luma axis and the saturation component represents the magnitude of the chroma vector. The combination of the values defines a hexagonal cone-shaped color space.
YCrCb, YUV, and YIQ are three formats that represent a color with a luma component Y, and two chroma components, Cr and Cb, U and V, or I and Q, respectively, that define a chroma vector. In a three-dimensional coordinate system, each component of either the YCrCb, YUV, and YIQ format represents a value along an axis, the combination of the values defining a cylindrical color space around the luma axis. The chroma components define the chroma vector. In data formats with a luma component, the luma component can be used independently to represent a pixel in a black and white image to be displayed, for example, with a black and white monitor.
A typical color modification in HSL color space may include increasing a color component or a combination of color components for all pixels in each digital image of a section of digital media. Typically, an editor accesses a segment of a composition that represents the section of media through an editor interface and inputs desired color modifications through the editor interface. Some systems permit an editor to apply color modifications to only portions of a digital image. Portions of a digital image also may be described as one or more pixels. For example, an editor may select with a mouse, keyboard, or some other editor input device a portion of the image and define color modifications for the selected portion. A suitable commercial system for color modification is Avid Media Illusion™ available from Avid Technology, Inc. The Avid Media Illusion Reference Guide, available from Avid Technology, Inc. is herein incorporated by reference. Other commercial software applications may be used.
Some systems permit an editor to define a color modification as a function of the luma of a pixel. Some systems also allow a user to define functions of luma that allow an editor to define the effect of a color modification over a range of possible luma values of a pixel. For example, an editor may define a highlight function that primarily affects high luma values, a midtone function that primarily affects mid-range luma values, and a shadow function that primarily affects low luma values. The editor may then associate a color modification with each function. If more than one function is defined over a range of luma values, each function, and thus a color modification associated with the function, may have a weighted effect for a given luma value. This weighted effect is defined by the value of the function for the given luma value normalized with respect to the values of functions for the given luma value. Although luma may be used to determine the weighting of the color modification, the color modification itself is not limited to adjusting the luma. Typical color modifications include adjustments to hue, saturation, luminance, brightness, contrast, gamma, tinting, etc.
For example, a color modification A is specified for a luma function defined by X=2L−2, and a color modification B is specified for a luma function defined by Y=0.5L+2. For pixel P with a luma value of 16,X=30 and Y=10. Normalizing X and Y, the weighted value of X is 0.75 and the weighted value of Y is 0.25. Thus, the color modification applied to pixel P is Z=0.75A+0.25B. The function used in this example is linear to simplify the explanation, but for decreasing and increasing the effect of a color modification for different values of luma, the function is usually non-linear.
The range of possible luma values may have ranges in which one of the functions has a predominant effect. For the highlight, midtone, and shadow functions described above, a highlight range is the range of luma values for which the highlight function has the strongest effect or the greatest weighted value, a midtone range is the range of luma values for which the midtone function has the strongest effect or the greatest weighted value, and the shadow range is the range of luma values for which the shadow function has the strongest effect or the greatest weighted value.
Some systems allow an editor to view a visual representation of the effect of more than one luma function on a digital image, where a selected luma function is emphasized. This representation generally is a substantially continuous gray scale image. In the gray scale image, pixels represented as white are pixels having a luma value for which the selected function has the strongest contribution. Pixels represented as black are pixels having a luma value for which the selected luma function has no contribution. All other pixels are represented as levels of gray between white and black, where the gray level representing the pixel is inversely proportional to the weighted value of the luma function for the luma value of the pixel. A suitable commercial product for defining luma functions, defining color modifications for each function, and viewing a representation of an image emphasizing a selected luma function is Avid Media Illusion ™ available from Avid Technology, Inc.

This patent is subject to a terminal disclaimer.

Multi-tone representation of a digital image on a digital nonlinear editing system


A flame-resistant, thermoplastic molding composition characterized by its improved stress cracking resistance, notched impact strength and heat resistance is disclosed. The composition contains

The present invention relates to polycarbonate/ABS moulding compositions which are rendered flame-resistant with phosphorus compounds and which have outstanding mechanical properties, in particular a high heat-resistance.
EP-A 0 640 655 describes moulding compositions consisting of aromatic polycarbonate, styrene-containing copolymers and graft polymers which can be rendered flame-resistant using monomeric and/or oligomeric phosphorus compounds.
EP-A 0 363 608 describes flame-resistant polymer mixtures consisting of aromatic polycarbonate, styrene-containing copolymer or graft copolymer as well as oligomeric phosphates as flame-resistant additives. For many applications, such as for example moulded articles inside housings, the heat resistance of these mixtures is often not adequate.
The object of the present invention is, therefore, to provide flame-resistant polycarbonate/ABS moulding compositions which have outstanding heat-resistance in addition to the high flame-resistance which is required.
Surprisingly, it has now been found that by using the mono- and/or oligo-phosphorus compounds according to the invention flame-resistant moulding compositions can be obtained which produce moulded items with very good mechanical properties and outstanding heat-resistance.
The present invention therefore provides flame-resistant, thermoplastic moulding compositions containing
A 5 to 95, preferably 10 to 90 parts by weight, in particular 20 to 80 parts by weight of aromatic polycarbonate or polyestercarbonate
B 1 to 60, preferably 1 to 40 parts by weight, in particular 2 to 30 parts by weight of at least 1 graft polymer of
B.1 5 to 95, preferably 20 to 60 wt. %, of one or more vinyl monomers on
B.2 5 to 95, preferably 40 to 80 wt. % of one or more graft substrates with a glass transition temperature below 10xc2x0 C., preferably 0xc2x0 C., in particular  less than xe2x88x9220xc2x0 C. and an average particle size (d50 value) of 0.05 to 5 xcexcm, preferably 0.20 to 0.35 xcexcm, in particular 0.25 to 0.30 xcexcm.
C 0 to 50, preferably 1 to 30, in particular 2 to 25 parts by weight of a thermoplastic vinyl (co)polymer
D 0.5 to 20 parts by weight, preferably 1 to 18 parts by weight, in particular 2 to 15 parts by weight, of at least one phosphorus compound of the general formula (I)
xe2x80x83in which
A independently of each other, represents halogen, preferably chlorine and/or bromine, a C1-C8 alkyl, preferably C1-C4 alkyl, in particular methyl, C6-C10 aryl, preferably phenyl, or C7-C12 aralkyl, preferably phenylxe2x80x94C1-C4 alkyl, in particular benzyl, group,
R1, R2, R3 and R4, independently of each other, represent an optionally halogenated C1-C8 alkyl group, or a C5-C6 cycloalkyl, C6-C20 aryl, or C7-C12 aralkyl group, each optionally substituted by halogen and/or a C1-C4 alkyl group,
y each, independently, is 0, 1, 2, 3 or 4,
n each, independently, is 0 or 1, preferably 1,
N is 0.3 to 30
and optionally further phosphorus compound(s) of the following formula (II)
xe2x80x83in which the groups R1, R2, R3, R4, n and N are defined as above and
x represents a mononuclear or polynuclear aromatic group with 6 to 30 carbon atoms, with the exception of diphenyl,
E 0.05 to 5 parts by weight, preferably 0.1 to 1 part by weight, in particular 0.1 to 0.5 parts by weight of a fluorinated polyolefin,
wherein the sum of the parts by weight of all the components A+B+C+D+E is 100.
Aromatic polycarbonates and/or aromatic polyestercarbonates in accordance with component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (to prepare aromatic polycarbonates see for example Schnell xe2x80x9cChemistry and Physics of Polycarbonatesxe2x80x9d Interscience Publishers 1964 as well as DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; and to prepare aromatic polyestercarbonates, e.g. DE-OS 3 077 934).
Aromatic polycarbonates are prepared e.g. by reacting diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, by the phase interface process, optionally using chain terminators, for example monophenols, and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols.
Diphenols for preparing aromatic polycarbonates and/or aromatic polyestercarbonates are preferably those of the formula (III)
wherein
A1 represents a single bond, a C1-C5 alkylene, C2-C5 alkylidene, C5-C6 cycloalkylidene, xe2x80x94Oxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94 or C6-C12 arylene group, which may be fused to further aromatic rings which may optionally contain heteroatoms, or a group of the formula
xe2x80x83or a group of the formula (V)
B independently of each other, represents a C1-C8 alkyl, preferably C1-C4 alkyl, in particular methyl, halogen, preferably chlorine and/or bromine, C6-C10 aryl, preferably phenyl, C7-C12 aralkyl, or phenyl-C1-C4 alkyl, preferably benzyl, group,
x each, independently, is 0, 1 or 2,
p is 1 or 0 and
R5 and R6 can be individually chosen for each Z, and independently of each other, represent hydrogen or a C1-C6 alkyl group, preferably hydrogen, methyl and/or ethyl,
Z is carbon, and
m is an integer, from 4 to 7, preferably 4 or 5,
with the proviso that R5 and R6 are both alkyl groups on at least one Z atom.
Preferred diphenols are hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, bis-(hydroxyphenyl)-C1-C5-alkanes, bis-(hydroxyphenyl)-C5-C6-cycloalkanes, bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-sulfoxides, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfones, xcex1,xcex1-bis-(hydroxyphenyl)-diisopropyl-benzenes such as their ring-brominated and/or ring-chlorinated derivatives.
Particularly preferred diphenols are 4,4-diphenylohenol, bisphenol-A, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4xe2x80x2-dihydroxydiphenyl sulfide, 4,4xe2x80x2-dihydroxydiphenyl-sulfone and their di- and tetrabrominated or chlorinated derivatives such as, for example, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
2,2-bis-(4-hydroxyphenyl)-propane (bisphenol-A) is particularly preferred.
The diphenols may be used individually or as any mixtures.
The diphenols are known from the literature or can be obtained using processes known from the literature.
Suitable chain terminators for preparing thermoplastic aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol, or 2,4,6-tribromophenol, but also long chain alkylphenols such as 4-(1,3-tetramethylbutyl)-phenol, in accordance with DE-OS 2 842 005 or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenyl, p-tert-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol. The amount of chain terminators to be used is generally between 0.5 and 10 mol. %, with respect to the molar sum of the particular diphenols used.
The thermoplastic aromatic polycarbonates have average weight-averaged molecular weights (Mw, determined e.g. by ultracentrifuge or light scattering measurements) of 10,000 to 200,000, preferably 20,000 to 80,000.
The thermoplastic aromatic polycarbonates may be branched in a known manner, in fact by the incorporation of 0.05 to 2.0 mol. %, with respect to the sum of diphenols used, of trifunctional or more than trifunctional compounds, for example those with three or more than three phenolic groups.
Homopolycarbonates or copolycarbonates are suitable. To prepare copolycarbonates according to the invention as component A, 1 to 25 wt. %, preferably 2.5 to 25 wt. % (with respect to the total amount of diphenols being used), of polydiorganosiloxanes with hydroxy-aryloxy terminal groups may also be used. These are known (see for example U.S. Pat. No. 3,419,634) or can be prepared using processes known from the literature. The preparation of polydiorganosiloxane-containing copolycarbonates is described e.g. in DE-OS 3 334 782.
Preferred polycarbonates, in addition to bisphenol-A homopolycarbonates, are copolycarbonates of bisphenol-A with up to 15 mol. %, with respect to the molar sum of diphenols, other than the diphenols mentioned elsewhere as preferred or particularly preferred compounds, in particular 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
Aromatic dicarboxylic acid dihalides for preparing aromatic polyestercarbonates are preferably diacid dichlorides of isophthalic acid, terephthalic acid, diphenylether-4,4xe2x80x2-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in the ratio between 1:20 and 20:1 are particularly preferred.
When preparing polyestercarbonates a carbonic acid halide, preferably phosgene, may also be used as a bifunctional acid derivative.
Suitable chain terminators for preparing aromatic polyestercarbonates, in addition to the monophenols already mentioned, are their chlorinated carbonates and the acid chlorides of aromatic monocarboxylic acids, which may optionally be substituted by C1-C22 alkyl groups or by halogen atoms and also aliphatic C2-C22 mono-carboxylic acid chlorides.
The amount of chain terminators is 0.1 to 10 mol. %, with respect to the moles of diphenols in the case of phenolic chain terminators or with respect to the moles of dicarboxylic acid dichlorides in the case of monocarboxylic acid chloride chain terminators.
Aromatic hydroxycarboxylic acids may also be incorporated into the aromatic polyestercarbonates.
The aromatic polyestercarbonates may be either linear or branched in a known manner (see also DE-OS 2 940 024 and DE-OS 3 007 934).
As branching agents, the following may be used in the amounts stated: trifunctional or more than trifunctional carboxylic acid chlorides such as trimesic trichloride, cyanuric acid trichloride, 3,3-4,4-benzophenonetetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride 0.01 to 1.0 mol. % (with respect to the dicarboxylic acid dichlorides used) or trifunctional or more than trifunctional phenols such as phloroglucine, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 4,4-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis-(4-hydroxyphenyl-isopropyl)-phenol, tetra-(4-hydroxyphenyl)-methane, 2,6-bis-(2-hydroxy-5-methylbenzyl)-4-methyl-phenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxy)-methane, 1,4-bis-[(4,4-dihydroxytriphenyl)-methyl]-benzene in amounts of 0.01 to 1.0 mol. %, with respect to the diphenols used. Phenolic branching agents may be initially introduced with the diphenols; acid chloride branching agents may be introduced together with the acid dichlorides.
The proportion of carbonate structural units in the thermoplastic aromatic polyestercarbonates may have any value at all.
The proportion of carbonate groups is preferably up to 100 mol. %, in particular up to 80 mol. %, especially up to 50 mol. %, with respect to the sum of ester groups and carbonate groups.
The ester and carbonate fractions in the aromatic polyestercarbonates may be present in the form of blocks or randomly distributed in the polycondensate.
The relative solution viscosity (xcex7rel) of the aromatic polyestercarbonates is in the range 1.18 to 1.4, preferably 1.22 to 1.3 (measured in solutions of 0.5 g of polyestercarbonate in 100 ml of methylene chloride solution at 25xc2x0 C.).
The thermoplastic aromatic polycarbonates and polyestercarbonates may be used individually or in any mixture with each other.
Component B in accordance with the invention is a graft polymer. These include graft copolymers with rubber-elastic properties which are substantially obtainable from at least two of the following monomers: chloroprene, 1,3-butadiene, isoprene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (meth)acrylates with 1 to 18 carbon atoms in the alcohol component; that is polymers such as are described e.g. in xe2x80x9cMethoden der Organischen Chemiexe2x80x9d (Houben-Weyl), Volume 14/1, Georg Thieme-Verlag, Stuttgart 1961, pages 393-406 and in C. B. Bucknall xe2x80x9cToughened Plasticsxe2x80x9d, Appl. Science Publishers, London 1977. Preferred polymers B are partially cross-linked and have gel contents of more than 20 wt. %, preferably more than 40 wt. %, in particular more than 60 wt. %.
Preferred graft polymers B are graft polymers of:
B.1 5 to 95, preferably 30 to 80, parts by weight of a mixture of
B.1.1 50 to 99 parts by weight of styrene, xcex1-methylstyrene, halogen or methyl ring-substituted styrenes, methyl methacrylate or mixtures of these compounds and
B.1.2 1 to 50 parts by weight of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, C1-C4 alkyl- or phenyl-N-substituted maleic imides or mixtures of these compounds on
B.2 5 to 95, preferably 20 to 70, parts by weight, of a polymer based on diene and/or alkyl acrylates with a glass transition temperature below xe2x88x9210xc2x0 C.
Preferred graft polymers B are e.g. substrates B.2 such as polybutadienes, butadiene/styrene copolymers and acrylate rubbers grafted with styrene and/or acrylonitrile and/or alkyl (meth)acrylates, i.e. copolymers of the type described in DE-OS 1 694 173 (=U.S. Pat. No. 3,564,077); or polybutadienes, butadiene/styrene or butadiene/acrylonitrile copolymers, polyisobutenes or polyisoprenes grafted with alkyl acrylates or alkyl methacrylates, vinyl acetate, acrylonitrile, styrene and/or alkylstyrenes, such as are described e.g. in DE-OS 2 348 377 (=U.S. Pat. No. 3,919,353).
Particularly preferred polymers B are e.g. ABS polymers such as are described e.g. in DE-OS 2 035 390 (=U.S. Pat. No. 3,644,574) or in DE-OS 2 248 242 (=GB-PS 1 409 275).
Particularly preferred graft polymers B are obtainable by a grafting reaction of
xcex1 10 to 70, preferably 15 to 50, in particular 20 to 40 wt. %, with respect to the graft polymer B, of at least one (meth)acrylate or 10 to 70, preferably 15 to 50, in particular 20 to 40 wt. %, of a mixture of 10 to 50, preferably 20to 35 wt. %, with respect to the mixture, of acrylonitrile or (meth)acrylate and 50 to 90, preferably 65 to 80 wt. %, with respect to the mixture, of styrene, as applied graft B.1, on
30 to 90, preferably 50 to 85, in particular 60 to 80 wt. %, with respect to graft polymer B, of a butadiene polymer with at least 50 wt. %, with respect to xcex2, of butadiene groups, as graft substrate B.2,
wherein the gel fraction of graft substrate P is preferably at least 70 wt. % (measured in toluene), the degree of grafting G is 0.15 to 0.55 and the average particle diameter d50 of the graft polymer B.2 is 0.05 to 2 xcexcm, preferably 0.1 to 0.6 xcexcm.
(Meth)acrylates xcex1 are esters of acrylic acid or methacrylic acid with monohydric alcohols with 1 to 18 carbon atoms. Methyl, ethyl and propyl methacrylate, n-butyl acrylate, t-butyl acrylate and t-butyl methacrylate are particularly preferred.
Graft substrate xcex2 may contain, in addition to butadiene groups, up to 50 wt. %, with respect to xcex2, of groups from other ethylenically unsaturated monomers such as styrene, acrylonitrile, esters of acrylic or methacrylic acid with 1 to 4 carbon atoms in the alcohol components (such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate), vinyl esters and/or vinyl ethers. The preferred graft substrate xcex2 consists of pure polybutadiene.
The degree of grafting G is the ratio by weight of grafted monomers to graft substrate and is dimensionless.
The average particle size d50 is the diameter above and below which 50 wt. % of the particle diameters are located. It may be determined by means of ultracentrifuge measurements (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972) 782-796).
Particularly preferred polymers B are also e.g. graft polymers of
xcfx84 20 to 90 wt. %, with respect to component B, of acrylate rubber with a glass transition temperature below xe2x88x9220xc2x0 C. as graft substrate B.2 and
xcex4 10 to 80 wt. %, with respect to component B, of at least one polymerisable ethylenically unsaturated monomer as graft monomer C.1.
Acrylate rubbers xcfx84 in polymers B are preferably polymers of alkyl acrylates, optionally with up to 40 wt. % with respect to xcfx84, of other polymerisable ethylenically unsaturated monomers. Preferred polymerisable acrylates include C1-C8 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; halogenated alkyl esters, preferably halogenated C1-C8 alkyl esters such as chloroethyl acrylate, and mixtures of these monomers.
In order to cross-link the product, monomers with more than one polymerisable double bond may be copolymerised. Preferred examples of cross-linking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with 3 to 12 carbon atoms or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms such as, for example, ethyleneglycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds such as, for example, trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as divinyl- and trivinylbenzene; but also triallyl phosphate and diallyl phthalate.
Preferred cross-linking monomers are allyl methacrylate, ethyleneglycol dimethylacrylate, diallyl phthalate and heterocyclic compounds which contain at least 3 ethylenically unsaturated groups.
Particularly preferred cross-linking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
The amount of cross-linking monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt. %, with respect to graft substrate xcfx84.
In the case of cyclic cross-linking monomers with at least 3 ethylenically unsaturated groups, it is advantageous to restrict the amount to less than 1 wt. % of the graft substrate xcfx84.
Preferred xe2x80x9cotherxe2x80x9d polymerisable ethylenically unsaturated monomers, apart from acrylates, which may optionally be used to prepare graft substrates xcfx84 are e.g. acrylonitrile, styrene, (x-methylstyrene, acrylaride, vinyl C1-C6 alkyl ethers, methyl methacrylate, butadiene. Preferred acrylate rubbers for use as graft substrates xcfx84 are emulsion polymers which have a gel content of at least 60 wt. %.
Further suitable graft substrates in accordance with B.2 are silicone rubbers with graft-active sites such as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
The gel content of graft substrate B.2 is determined at 25xc2x0 C. in dimethylformamide (M. Hoffmann, H. Krxc3x6mer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
Graft polymer B may be prepared by known processes such as bulk, suspension, emulsion or bulk-suspension processes.
Since, as is known, the grafting monomers cannot be grafted onto the grafting substrate completely and absolutely during the grafting reaction, graft polymers B according to the invention are also understood to be those products which are obtained by the polymerisation of graft monomers in the presence of the graft substrate.
The average particle size d50 is the diameter above and below which 50% of the particle diameters are located. It may be determined by means of ultracentrifuge measurements (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972) 782-1796).
Since, as is known, the grafting monomers cannot be grafted onto the grafting substrate completely and absolutely during the grafting reaction, graft polymers B according to the invention are also understood to be those products which are obtained by the (co)polymerisation of graft monomers in the presence of the graft substrate and which are also present after any working-up procedures.
Component C comprises at least one thermoplastic vinyl (co)polymer.
Polymers which are suitable for use as (co)polymers C are those made from at least one monomer from the group of vinyl aromatic compounds, vinyl cyanides such as unsaturated nitrites, C1-C8-alkyl (meth)acrylates, unsaturated carboxylic acids and derivatives such as anhydrides and imides of unsaturated carboxylic acids.
(Co)polymers made from
C.1 50 to 99 parts by weight of vinyl aromatic compounds and/or ring-substituted vinyl aromatic compounds, such as, for example, styrene, xcex1-methylstyrene, p-methylstyrene, p-chlorostyrene and/or (C1-C4)-alkyl methacrylates such as e.g. methyl methacrylate, ethyl methacrylate, and
C.2 1 to 50 parts by weight of vinyl cyanides such as unsaturated nitrites, for example acrylonitrile and methacrylonitrile and/or (C1-C8)-alkyl (meth)acrylates, e.g. methyl methacrylate, n-butyl acrylate, t-butyl acrylate and/or unsaturated carboxylic acids such as maleic acid and/or derivatives such as anhydrides and imides of unsaturated carboxylic acids, such as for example maleic anhydride and N-phenylmaleic imide, are particularly suitable.
The (co)polymers C are resinous, thermoplastic and rubber-free.
Copolymers of C.1 styrene and C.2 acrylonitrile are particularly preferred.
(Co)polymers in accordance with C are known and can be prepared by radical poly-merisation, in particular by emulsion, suspension, solution or bulk polymerisation. (Co)polymers in accordance with component C preferably have molecular weights Mw (weight average, determined by light scattering or sedimentation) of between 15,000 and 200,000.
(Co)polymers in accordance with component C frequently arise as by-products during the graft polymerisation of component B, in particular if large amounts of monomers B.1 are grafted onto small amounts of rubber B.2.The amount of C optionally also used according to the invention does not include these by-products from the graft polymerisation of B.
If component C is present in the moulding compositions, then the ratio by weight of components B to C is between 2:1 and 1:4, preferably between 1:1 and 1:2, in order to achieve the desired mechanical properties for specific purposes.
Moulding compositions according to the invention contain, as flame-resistant agents, at least one organic phosphorus compound of the formula (I).
In the formula, the groups R1, R2, R3, R4 and A as well as n and y are defined in the same way as given above. The aromatic groups R1, R2, R3 and R4 and A for their part may be substituted by halogen and/or alkyl groups, preferably chlorine, bromine and/or C1-C4 alkyl groups. Particularly preferred aryl groups are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
N may have a value from 0.3 to 30, preferably an average value of 0.3 to 20, particularly preferably 0.5 to 10, most preferably 0.5 to 6. When mixtures of phosphorus compounds are present, N may have the average values given above. Monophosphorus compounds and/or oligomeric phosphorus compounds may be contained in this mixture. In the event that N=0, formula (I) describes monophosphorus compounds.
Some of compound D may be replaced (at most 75 wt. %) by at least one mono- and/or oligo- and/or polyphosphorus compound of the formula (II), which differs from compounds of the formula (I)
and in which the groups R1, R2, R3, R4, n and N are defined in the same way as above and
X in formula (II) represents a mononuclear or polynuclear aromatic group with 6 to 30 carbon atoms, with the exception of diphenyl. The group is derived from diphenols in accordance with formula (III) such as e.g. bisphenol-A, resorcinol or hydroquinone or their chlorinated or brominated derivatives.
Mixtures of phosphorus compounds of the formula (I), preferably mono- and/or oligomeric phosphates of the formula (1), with N values of 0.5 to 10, in particular 0.5 to 6, are preferably used as component D.
Monomeric and oligomeric phosphorus compounds of the formula (I) in the mixture are preferably chosen so that a synergistic effect is produced. The mixture generally consists of 10 to 90 wt. % of oligomers and 90 to 10 wt. % of monophosphorus compounds of the formula (I). Monomeric phosphorus compounds and/or monophosphate compounds are preferably mixed within the range from 12 to 50, preferably 14 to 40, in particular 15 to 40 wt. %, with the complementary amount of oligomeric phosphate compounds.
Suitable monophosphorus compounds, i.e. N=0, are tributylphosphate, tris-(2-chloroethyl) phosphate, tris-(2,3-dibromopropyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri-(isopropylphenyl) phosphate, halogen substituted aryl phosphates, dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl phenylphosphonate, triphenylphosphine oxide and/or tricresylphosphine oxides.
Phosphorus compounds in accordance with component D are generally known organic compounds or can be prepared by known methods in an analogous manner (see e.g. Ullmanns Encyklopxc3xa4die der technischen Chemie, Vol. 18, page 301 et seq 179; Houben-Weyl, Methoden der organischen Chemie, Vol. 12/1, p. 43; Beistein Vol. 6, p. 177).
Fluorinated polyolefins E are high molecular weight compounds and have glass transition temperatures above xe2x88x9230xc2x0 C., generally above 100xc2x0 C., fluorine contents of preferably 65 to 76, in particular 70 to 76 wt. %, average particle diameters d50 of 0.05 to 1000, preferably to 0.08 to 20 xcexcm. In general, the fluorinated polyolefins E have a density of 1.2 to 2.3 g/cm3. Preferred fluorinated polyolefins E are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene/ hexafluoropropylene copolymers and ethylene/tetrafluoroethylene copolymers. Fluorinated polyolefins are known (see xe2x80x9cVinyl and Related Polymersxe2x80x9d by Schildknecht, John Wiley and Sons, Inc., New York, 1962, pp 484-494; xe2x80x9cFluoropolymersxe2x80x9d by Wall, Wiley-Interscience, John Wiley and Sons Inc., New York, Vol. 13, 1970, pp 623-654; xe2x80x9cModern Plastics Encyclopediaxe2x80x9d 1970 to 1971, Vol. 47, No. 10A, October 1970, McGraw-Hill, Inc., New York, pp 134 and 774; xe2x80x9cModem Plastics Encyclopediaxe2x80x9d 1975 to 1976, October 1975, Vol. 52, No. 10A, McGraw-Hill, Inc., New York, pp 27, 28 and 472 and U.S. Pat. Nos. 3,671,487, 3 723 373 and 3,838,092).
They can be prepared by known processes, for example by polymerisation of tetrafluoroethylene in aqueous medium with a free radical-forming catalyst, for example sodium, potassium or ammonium peroxydisulfate at pressures of 7 to 71 kg/cm2 and at temperatures of 0 to 200xc2x0 C., preferably at temperatures of 20 to 100xc2x0 C. (See e.g. U.S. Pat. No. 2,393,967 for more details). Depending on the form actually used, the density of these materials may be between 1.2 and 2.3 g/cm3 and the average particle size between 0.5 and 1000 xcexcm.
Preferred fluorinated polyolefins E according to the invention are tetrafluoroethylene polymers and have average particle diameters of 0.05 to 20 xcexcm, preferably 0.08 to 10 xcexcm, and a density of 1.2 to 1.9 g/cm3 and are preferably used in the form of a coagulated mixture of emulsions of tetrafluoroethylene polymers E with emulsions of graft polymers B.
Suitable fluorinated polyolefins E which can be used in a powder form are tetrafluoroethylene polymers with average particle diameters of 100 to 1000 xcexcm and densities of 2.0 g/cm3 to 2.3 g/cm3.
To prepare a coagulated mixture of B and E, an aqueous emulsion (latex) of a graft polymer B is first mixed with a finely divided emulsion of a fluorinated polyolefin E; suitable emulsions of fluorinated polyolefin generally have solids contents of 30 to 70 wt. %, preferably 50 to 60 wt. %, in particular 30 to 35 wt. %.
The data given on amounts in the description of component B does not include the proportion of graft polymer in the coagulated mixture of graft polymer and fluorinated polyolefins.
In the emulsion mixture, the ratio by weight of graft polymer B to fluorinated polyolefin E is 95:5 to 60:40. The emulsion mixture is coagulated in a known manner, for example by spray drying, freeze drying or coagulating by adding inorganic or organic salts, acids, bases or organic water-miscible solvents such as alcohols or ketones, preferably at temperatures of 20 to 150xc2x0 C. in particular 50 to 100xc2x0 C. If required drying may be performed at 50 to 200xc2x0 C. , preferably 70 to 100xc2x0 C.
Suitable tetrafluoroethylene polymer emulsions are commercially available products and are provided for example by Du Pont as Teflon 30 N.
Moulding compositions according to the invention may contain at least one of the conventional additives such as lubricants, mould release agents, nucleating agents, anti-static agents, stabilisers and dyes, pigments and/or reinforcing materials. Suitable inorganic reinforcing materials are glass fibres, optionally cut up or milled, glass beads, glass spheres, reinforcing materials in the form of platelets such as kaolin, talc, mica, carbon fibres. Cut up or milled glass fibres are preferred as reinforcing materials, preferably with a length of 1 to 10 mm and a diameter of less than 20 xcexcm, in an amount of 1 to 40 parts by weight; the glass fibres are preferably surface-treated.
Moulding compositions according to the invention may also contain at least one polar compound of at least one metal from groups 1A to 5A and 1B to 8 of the periodic system with at least one element chosen from the group oxygen, sulfur, boron, carbon, phosphorus, nitrogen, hydrogen and silicon, as very finely divided inorganic powders. An oxide or hydroxide, preferably TiO2, SiO2, SnO2, ZnO, boehmite, ZrO2, Al2O3, iron oxides, their mixtures and doped compounds are preferably used as a polar compound, in particular boehmite or TiO2, with an average particle diameter of less than 200 nm, preferably 0.1 to 100 nm, in particular 1 to 50 nm.
Moulding compositions according to the invention may contain one or more further optionally synergistic flame-resistant agents. The following may be mentioned by way of example as further flame-resistant agents: organic halogen compounds such as decabromobisphenylether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine-formaldehyde resins, inorganic hydroxide compounds such a Mg or Al hydroxide, inorganic compounds such as antimony oxides, barium metaborate, hydroxy-antimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate and tin oxide as well as siloxane compounds. These flame-resistant agents are generally added in amounts of 0.01 to 35 wt. % (with respect to the total moulding composition).
Moulding compositions according to the invention containing components A to E and optionally other known additives such as stabilisers, dyes, pigments, lubricants and mould release agents, nucleating agents, nano-particles and anti-static agents and reinforcing materials and flame-resistant agents are prepared by mixing the particular constituents in a known manner and melt-compounding or melt-extruding at temperatures of 200xc2x0 C. to 300xc2x0 C. in conventional equipment such as internal compounders, extruders and twin shaft screws, wherein component E is preferably used in the form of the coagulated mixture mentioned above.
Mixing the individual constituents may be performed in a known manner, either in sequence or simultaneously, in fact either at about 20xc2x0 C. (room temperature) or at a higher temperature.
Moulding compositions according to the present invention may be used to produce moulded items of any type. Moulded items may be produced in particular by injection moulding. Examples of moulded items which may be prepared are: housing parts of any type, e.g. for domestic equipment such as juice extractors, coffee machines, mixers, for office machines such as monitors, printers or copiers, or cladding sheets for the building sector and parts for the automobile sector. They may also be used in the area of electrical engineering because they have very good electrical properties.
The moulding compositions are particularly suitable for producing moulded parts where particularly high specifications with respect to heat resistance of the plastics used are required.
Another form of processing is to produce moulded items by thermoforming from previously prepared sheets or films.
The present invention also provides use of the moulding compositions according to the invention to produce moulded items of any type, preferably those mentioned above, and the moulded items produced from the moulding compositions according to the invention.

Flame-resistant thermostable polycarbonate ABS moulding materials

Abstract: A) an aromatic polycarbonate or polyestercarbonate,

Abstract: B) a graft polymer of B.1 5 to 95 wt. % of one or more vinyl monomers on B.2 5 to 95 wt. % of one or more graft substrates with a glass transition temperature below 10xc2x0 C. and an average particle size (d50 value) of 0.05 to 5 xcexcm,

Abstract: C) 0 to 50 parts by weight of a thermoplastic vinyl copolymer,

Abstract: D) 0.5 to 20 parts by weight of at least one phosphorus compound of the general formula (I) and optionally at least one further phosphorus compound which differs from compounds of the formula (I), and

Abstract: E) 0.05 to 5 parts by weight of a fluorinated polyolefin.