A photographic element having a layer comprising a silver halide emulsion, a 1-aryl-4-aryloxy-2-pyrazolin-5-one magenta dye forming coupler, and a sulfide, sulfoxide or sulfone compound. Such elements exhibit good activity and stability of the magenta coupler. Preferably, the foregoing magenta dye forming coupler has the structure of Ia or Ib below, while the sulfide, sulfoxide and sulfone compounds have the structure VI, VII or VIII below:

The present invention relates to photographic elements having a layer containing both a 1-aryl-4-aryloxy-2-pyrazolin-5-one magenta coupler, and a sulfide, sulfoxide or sulfone compound.
In a silver halide photographic element, a color image is formed when the material is exposed to light and then subjected to color development with a primary amine developer. The color development results in imagewise reduction of silver halide and production of oxidized developer. The oxidized primary amine developer subsequently reacts with one or more incorporated dye-forming couplers to form dye in an imagewise fashion. Some couplers, referred to as DIR couplers, release a development inhibitor compound or fragment upon coupling with the oxidized primary amine developer. Further, some of these DIR couplers release the inhibitor compound or fragment with a time delay. These are sometimes referred to as DIAR couplers.
A variety of magenta dye-forming coupler types have been used in color photographic materials. These include pyrazoloazole couplers, 1-phenyl-3-acylamino-2-pyrazolin-5-one couplers and 1-phenyl-3-anilino-2pyrazolin-5-one couplers. U.S. Pat. Nos. 3,419,391, 3,519,429 and 4,248,962, 4,585,728, 4,692,529, 4,724,198, and 4,977,073 disclose couplers which include 1-aryl-4-aryloxy-2-pyrazolin-5-one type couplers.
Many compounds, including sulfur-containing addenda, have been previously tried or suggested for use in conjunction with couplers in an effort to improve coupler activity. For example, Rody et al disclose cyclic sulfide, sulfoxide and sulfone stabilizers in U.S. Pat. Nos. 4,933,271, 5,006,665 and 5,070,007. Cyclic sulfoxide and sulfone stabilizers are also disclosed in U.S. Pat. No. 5,017,465. Sulfone-containing addenda are used in combination with magenta dye-forming couplers in U.S. Pat. No. 4,770,987. Yamada et al disclose combinations of magenta dye-forming couplers, phenolic compounds and sulfide or sulfoxide compounds in U.S. Pat. No. 4,113,488. Combinations of sulfoxide or sulfone compounds and pyrazolotriazole magenta dye-forming couplers are disclosed in U.S. Pat. No. 5,232,821 of Merkel et al.
Magenta dye-forming coupler compositions of high activity that efficiently react with oxidized developer are, however, still needed. There is also a need for magenta dye-forming DIR (including DIAR) coupler compositions that efficiently release development inhibitors.
It has been found that while 1-aryl-4-aryloxy-2pyrazolin-5-one type couplers can have high activity and high dye forming ability, such couplers tend to be unstable toward aerial oxidation and are therefore impractical. While various compounds might be considered for use with such couplers in an attempt to alleviate the foregoing problem, we have found that surprisingly certain sulfide, sulfoxide or sulfone addenda when used in combination with 1-aryl-4-aryloxy-2-pyrazolin-5-one magenta dye-forming couplers can dramatically improve their oxidative stability.
The present invention therefore provides a photographic element comprising a silver halide emulsion having a layer comprising a silver halide emulsion, a 1-aryl-4-aryloxy-2pyrazolin-5-one magenta dye forming coupler, and a sulfide, sulfoxide or sulfone compound.
Embodiments of the Invention
In the present invention, it is preferred that the magenta dye forming coupler has structure Ia or Ib, below, and the sulfide, sulfoxide or sulfone compounds have structures VI, VII and VIII, respectively:
wherein:
R1 is an aryl group;
R2 is an alkyl group, an acylamino group, an anilino group, a carbamoyl group or an alkoxy group;
R3 is a substituent any of which may be the same or different; and
n is an integer from 0 to 4;
wherein:
R8 and R9 are independently an alkyl group, an alkylene group, an alkenyl group or an aryl group, or R8 and R9 may together form a ring including the sulfur atom, the total number of carbon atoms in R8 and R9 together being at least 12.
It should be noted that throughout this application a reference to any type of xe2x80x9cgroupxe2x80x9d includes both the unsubstituted and substituted group described. Various substituents can include known substituents, such as halogen (for example, chloro, fluoro, bromo, iodo), alkoxy (for example, methoxy, ethoxy), substituted or unsubstituted alkyl (for example, methyl, trifluoromethyl), alkenyl, thioalkyl (for example, methylthio or ethylthio), substituted and unsubstituted aryl (for example, phenyl, thienyl, furyl, pyrrolyl) and others known in the art. Alkyl substituents may specifically include xe2x80x9clower alkylxe2x80x9d, that is having from 1 to 6 carbon atoms, for example, methyl, ethyl, and the like. Additionally, substituents may form bridged linkages. Further, with regard to any alkyl group, alkylene group or alkenyl group, it will be understood that these can be branched or unbranched and include ring structures.
Preferably R2 is an alkyl group. Especially preferred are couplers of structure Ia or Ib, in which R2 is of structure IIa or IIb, below:
wherein:
R4 is hydrogen, an alkyl group or an aryl group;
R5 is an aryl group or an alkyl group; and
X is an amino group, an anilino group, a carbonamido group, a sulfonamido group, an acyloxy group, an alkoxy carbonyl group, a carbamoyl group, a sulfamoyl group, an alkylthio group, an arylthio group, an alkyl sulfoxide group, an aryl sulfoxide group, an alkyl sulfonyl group or an aryl sulfonyl group.
It is preferable that the total number of carbon atoms in R1, R2 and R3 taken together be at least 14, and more preferably at least 16 to minimize coupler water solubility and wandering.
An anilino group for R2 is less preferred because it tends to reduce coupler stability toward aerial oxidation. When R2 is an acylamino or an anilino group, it is preferred that at least one R3 is an electron-withdrawing group to improve coupler stability. Electron withdrawing groups are discussed in March, Advanced Organic Chemistry, pages 20-21, 228-229, 386-387, 494-497. In particular, preferred electron withdrawing substituents would have a Hammett "sgr"p constant of greater than 0.1 and preferably between 0.1 and 1.0 (for example, between any of 0.3, 0.4, 0.5 or 0.6 and 1.0). Hammett "sgr"p values are discussed in Advanced Organic Chemistry 3rd Ed., J. March, (John Wiley Sons, NY; 1985). Note that the xe2x80x9cpxe2x80x9d subscript refers to the fact that the "sgr" values are measured with the substituents in the para position of a benzene ring. Additional tables relating to Hammett "sgr"p constants can be found in Chemical Reviews Volume 91, pages 165-195 (authored by C Hansch et al.). Examples of electron-withdrawing groups include nitro, cyano, sulfamoyl, sulfonamido, alkylsulfonyl, arylsulfonyl, carbamoyl, carbonamido, alkoxycarbonyl, aryloxycarbonyl and trifluoromethyl groups and halogen atoms, such as chlorine and fluorine.
Also particularly useful for the practice of this invention are development inhibitor-releasing couplers in which one of R3 contains a development inhibitor group that is released after the aryloxy group couples off when the 1-aryl-4-aryloxy-2-pyrazolin-5-one coupler reacts with oxidized developer. Particularly useful inhibitor-releasing couplers of structure Ia or Ib are those in which the 4-aryloxy coupling-off group shown in formula Ia or Ib is of structure III, IV or V, below:
wherein
Q and W are electron-withdrawing groups, any of which may be the same or different;
p is 0, 1 or 2;
m is 0 or 1;
R6 is hydrogen, phenyl or an alkyl group; and
R7 is an alkyl group containing 1 to 10 carbon atoms or a phenyl group; and
IN is a development inhibitor moiety.
In formulae IV and V above, Q is preferably in the para position with respect to the oxygen.
Development inhibitor moieties, IN, useful for the couplers of this invention include oxazoles, thiazoles, diazoles, triazoles, oxadiazoles, thiadiazoles, oxathiazoles, thiatriazoles, benzotriazoles, tetrazoles, benzimidazoles, indazoles, isoindazoles, mercaptotetrazoles, selenotetrazoles, mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazoles, mercaptobenzimidazoles, selenobenzimidazoles, benzodiazoles, mercaptooxazoles, mercaptothiadiazoles, mercaptothiazoles, mercaptotriazoles, mercaptooxadiazoles, mercaptodiazoles, mercaptooxathiazoles, tellurotetrazoles and benzisodiazoles.
With regard to the sulfides, sulfoxides and sulfones of this invention described above, as already mentioned when R8 or R9 is an alkyl group, an alkylene group, an alkenyl group any of those groups can be branched or unbranched and include ring structures. Substituents which may be present on R8 or R9 when they are alkyl, alkylene or alkenyl groups, include one or more substituents selected from the group consisting of aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, acyloxy, carbonamido, carbamoyl, sulfonamido and sulfamoyl groups and halogen atoms. When R8 or R9 is an aryl group, substituents which may be present include substituents selected from the group consisting of alkyl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, acyloxy, carbonamido, carbamoyl, sulfonamido, sulfamoyl groups and halogen atoms.
Preferably, both R8 and R9 are unsubstituted alkyl groups, which may be either unbranched or branched. It is also preferred that the total number of carbon atoms in R8 and R9 be at least 16 to minimize water solubility and wandering of the sulfide, sulfoxide or sulfone compound. Sulfides of formula VI and sulfoxides of formula VII are preferred for their stabilizing ability.
With regard to the location of the coupler and sulfur containing compound, preferably they are together in the same dispersion (specifically, in the same drops of a solvent dispersion, typically the coupler solvent, in the layer).
Useful coated levels of the 1-aryl-4-aryloxy-2-pyrazolin-5-one magenta dye-forming couplers of the invention range from about 0.005 to 2.0 g/sq m, depending on the coupler type (note xe2x80x9csq mxe2x80x9d=square meters). Imaging couplers would typically be coated in the 0.05 to 2.00 g/sq m range (preferably 0.10-1.00 g/sq m), while inhibitor-releasing couplers would typically be used in the 0.005 to 0.50 g/sq m range (preferably 0.01-0.25 g/sq m). Useful coated mole ratios of the 1-aryl-4-aryloxy-2pyrazolin-5-one couplers to sulfide, sulfoxide or sulfone compound range from about 1:0.05 to about 1:5, or more typically from about 1:0.1 to about 1:2.
The couplers of this invention are usually utilized by dissolving them in high-boiling coupler solvents and then dispersing the organic coupler plus coupler solvent mixtures as small particles (in particular, droplets) in aqueous solutions of gelatin and surfactant (via milling or homogenization). Removable auxiliary organic solvents such as ethyl acetate or cyclohexanone may also be used in the preparation of such dispersions to facilitate the dissolution of the coupler in the organic phase. The sulfides, sulfoxides or sulfone compounds of this invention may serve as the sole high-boiling solvents for the 1-aryl-4-aryloxy-2pyrazolin-5-one couplers of this invention. Alternatively, other high-boiling coupler solvents may be used together with the sulfides, sulfoxide or sulfone compounds of this invention, including aryl phosphates (e.g. tritolyl phosphate), alkyl phosphates (e.g. trioctyl phosphate), mixed aryl alkyl phosphates (e.g. diphenyl 2-ethylhexyl phosphate), aryl, alkyl or mixed aryl alkyl phosphonates, phosphine oxides (e.g. trioctylphosphine oxide), esters of aromatic acids (e.g. dibutyl phthalate, octyl benzoate, or benzyl salicylate) esters of aliphatic acids (e.g. acetyl tributyl citrate or dibutyl sebecate), alcohols (e.g. 2-hexyl-1-decanol), carbonamides (e.g. N,N-dibutyldodecanamide or N-butylacetanilide), sulfonamides (e.g. N,N-dibutyl-p-toluenesulfonamide) or hydrocarbons (e.g. dodecylbenzene). It is preferred that the 1-aryl-4-aryloxy-2pyrazolin-5-one coupler plus sulfide, sulfoxide or sulfone combinations of this invention not be coated with a phenol coupler solvent or other phenol compound in the same dispersion (that is, in the same droplets of a dispersion) or same layer.
An alternate embodiment of the present invention provides a 1-aryl-4-aryloxy-2pyrazolin-5-one magenta dye forming coupler which has a sulfoxide group. Such a coupler may be used with or without the sulfide, sulfoxide or sulfone compounds described above. The foregoing coupler could be the same as any of those described above for use with the sulfide, sulfoxide or sulfone compounds described. The substituents on the sulfoxide could include any of those groups described above for R8 and R9.
Examples of 1-aryl-4-aryloxy-2pyrazolin-5-one magenta dye-forming couplers useful for the practice of this invention include, but are not limited to, A1-A21, below:
Examples of sulfide, sulfoxide and sulfone compounds useful for the practice of the present invention include, but are not limited to, S1-S26 below:
The photographic elements of the present invention can be single color elements or multicolor elements. Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In a alternative format, the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.
A typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler. The element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like. All of these can be coated on a support which can be transparent or reflective (for example, a paper support). While the order of the color sensitive layers can be varied, they will normally be red-sensitive, green-sensitive and blue-sensitive, in that order on a transparent support, with the reverse order on a reflective support being typical.
In the following discussion of suitable materials for use in elements of this invention, reference will be made to Research Disclosure, December 1989, Item 308119, published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire P010 7DQ, ENGLAND, which will be identified hereafter by the term xe2x80x9cResearch Disclosure I.xe2x80x9d The Sections hereafter referred to are Sections of the Research Disclosure I.
The silver halide emulsions employed in the elements of this invention can be either negative-working or positive-working. Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I through IV. Color materials and development modifiers are described in Sections V and XXI. Vehicles which can be used in the elements of the present invention are described in Section IX, and various additives such as brighteners, antifoggants, stabilizers, light absorbing and scattering materials, hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections V, VI, VIII, X, XI, XII, and XVI. Manufacturing methods are described in Sections XIV and XV, other layers and supports in Sections XIII and XVII, processing methods and agents in Sections XIX and XX, and exposure alternatives in Section XVIII.
Preferred color developing agents are p-phenylenediamines. Especially preferred are:
4-amino N,N-diethylaniline hydrochloride,
4-amino-3-methyl-N,N-diethylaniline hydrochloride,
4-amino-3-methyl-N-ethyl-N-(xcex2-(methanesulfonamido)ethyl)aniline sesquisulfate hydrate,
4-amino-3-methyl-N-ethyl-N-(xcex2-hydroxyethyl)aniline sulfate,
4-amino-3-xcex2-(methanesulfonamido)ethyl-N,N -diethylaniline hydrochloride and
4-amino-N-ethyl-N-(2-methoxyethyl)-m -toluidine di-p-toluene sulfonic acid.
With negative working silver halide a negative image can be formed. Optionally a positive (or reversal) image can be formed.
The photographic elements of the present may also use colored couplers (e.g. to adjust levels of interlayer correction) and masking couplers such as those described in EP 213.490; Japanese Published Application 58-172,647; U.S. Pat. No. 2,983,608; German Application DE 2,706,117C; U.K. Patent 1,530,272; Japanese Application A-113935; U.S. Pat. No. 4,070,191 and German Application DE 2,643,965. The masking couplers may be shifted or blocked.
The photographic elements may also contain materials that accelerate or otherwise modify the processing steps of bleaching or fixing to improve the quality of the image. Bleach accelerators described in EP 193,389; EP 301,477; U.S. Pat. Nos. 4,163,669; 4,865,956; and 4,923,784 are particularly useful. Also contemplated is the use of nucleating agents, development accelerators or their precursors (UK Patent 2,097,140; U.K. Patent 2,131,188); electron transfer agents (U.S. Pat. Nos. 4,859,578; 4,912,025); antifogging and anti color-mixing agents such as derivatives of hydroquinones, aminophenols, amines, gallic acid; catechol; ascorbic acid; hydrazides; sulfonamidophenols; and non color-forming couplers.
The elements may also contain filter dye layers comprising colloidal silver sol or yellow and/or magenta filter dyes, either as oil-in-water dispersions, latex dispersions or as solid particle dispersions. Additionally, they may be used with xe2x80x9csmearingxe2x80x9d couplers (e.g. as described in U.S. Pat. No. 4,366,237; EP U.S. Pat. Nos. 96,570; 4,420,556; and 4,543,323.) Also, the couplers may be blocked or coated in protected form as described, for example, in Japanese Application 61/258,249 or U.S. Pat. No. 5,019,492.
In addition to the aryloxypyrazolone couplers of the present invention, the photographic elements may further contain other image-modifying compounds such as xe2x80x9cDeveloper Inhibitor-Releasingxe2x80x9d compounds (DIR""s). Useful additional DIR""s for elements of the present invention, are known in the art and examples are described in U.S. Pat. Nos. 3,137,578; 3,148,022; 3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506; 3,617,291; 3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095,984; 4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437; 4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634; 4,579,816; 4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601; 4,791,049; 4,857,447; 4,865,959; 4,880,342; 4,886,736; 4,937,179; 4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835; 4,985,336 as well as in patent publications GB 1,560,240; GB 2,007,662; GB 2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE 3,644,416 as well as the following European Patent Publications: 272,573; 335,319; 336,411; 346, 899; 362, 870; 365,252; 365,346; 373,382; 376,212; 377,463; 378,236; 384,670; 396,486; 401,612; 401,613.
DIR compounds are also disclosed in xe2x80x9cDeveloper-Inhibitor-Releasing (DIR) Couplers for Color Photography,xe2x80x9d C. R. Barr, J. R. Thirtle and P. W. Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969), incorporated herein by reference.
It is also contemplated that the concepts of the present invention may be employed to obtain reflection color prints as described in Research Disclosure, November 1979, Item 18716, available from Kenneth Mason Publications, Ltd, Dudley Annex, 12a North Street, Emsworth, Hampshire P0101 7DQ, England, incorporated herein by reference. The emulsions and materials to form elements of the present invention, may be coated on pH adjusted support as described in U.S. Pat. No. 4,917,994; with epoxy solvents (EP 0 164 961); with additional stabilizers (as described, for example, in U.S. Pat. Nos. 4,346,165; 4,540,653 and 4,906,559); with ballasted chelating agents such as those in U.S. Pat No. 4,994,359 to reduce sensitivity to polyvalent cations such as calcium; and with stain reducing compounds such as described in U.S. Pat. Nos. 5,068,171 and 5,096,805. Other compounds useful in the elements of the invention are disclosed in Japanese Published Applications 83-09,959; 83-62,586; 90-072,629, 90-072,630; 90-072,632; 90-072,633; 90-072,634; 90-077,822; 90-078,229; 90078,230; 90-079,336; 90-079,338; 90-079,690; 90079,691; 90-080,487; 90-080,489; 90-080,490; 90080,491; 90-080,492; 90-080,494; 90-085,928; 90086,669; 90-086,670; 90-087,361; 90-087,362; 90087,363; 90-087,364; 90-088,096; 90-088,097; 90093,662; 90-093,663; 90-093,664; 90-093,665; 90093,666; 90-093,668; 90-094,055; 90-094,056; 90101,937; 90-103,409; 90-151,577.
The silver halide used in the photographic elements of the present invention may be silver bromoiodide, silver bromide, silver chloride, silver chlorobromide, silver chlorobromo-iodide, and the like. The type of silver halide grains preferably include polymorphic, cubic, and octahedral. The grain size of the silver halide may have any distribution known to be useful in photographic compositions, and may be ether polydipersed or monodispersed. Particularly useful in this invention are tabular grain silver halide emulsions. Specifically contemplated tabular grain emulsions are those in which greater than 50 percent of the total projected area of the emulsion grains are accounted for by tabular grains having a thickness of less than 0.3 micron (0.5 micron for blue sensitive emulsion) and an average tabularity (T) of greater than 25 (preferably greater than 100), where the term xe2x80x9ctabularityxe2x80x9d is employed in its art recognized usage as
T=ECD/t2
where
ECD is the average equivalent circular diameter of the tabular grains in microns and
t is the average thickness in microns of the tabular grains.
The average useful ECD of photographic emulsions can range up to about 10 microns, although in practice emulsion ECD""s seldom exceed about 4 microns. Since both photographic speed and granularity increase with increasing ECD""s, it is generally preferred to employ the smallest tabular grain ECD""s compatible with achieving aim speed requirements.
Emulsion tabularity increases markedly with reductions in tabular grain thickness. It is generally preferred that aim tabular grain projected areas be satisfied by thin (t less than 0.2 micron) tabular grains. To achieve the lowest levels of granularity it is preferred to that aim tabular grain projected areas be satisfied with ultrathin (t less than 0.06 micron) tabular grains. Tabular grain thicknesses typically range down to about 0.02 micron. However, still lower tabular grain thicknesses are contemplated. For example, Daubendiek et al U.S. Pat. No. 4,672,027 reports a 3 mole percent iodide tabular grain silver bromoiodide emulsion having a grain thickness of 0.017 micron.
As noted above tabular grains of less than the specified thickness account for at least 50 percent of the total grain projected area of the emulsion. To maximize the advantages of high tabularity it is generally preferred that tabular grains satisfying the stated thickness criterion account for the highest conveniently attainable percentage of the total grain projected area of the emulsion. For example, in preferred emulsions tabular grains satisfying the stated thickness criteria above account for at least 70 percent of the total grain projected area. In the highest performance tabular grain emulsions tabular grains satisfying the thickness criteria above account for at least 90 percent of total grain projected area.
Suitable tabular grain emulsions can be selected from among a variety of conventional teachings, such as those of the following: Research Disclosure, Item 22534, January 1983, published by Kenneth Mason Publications, Ltd., Emsworth, Hampshire P010 7DD, England; U.S. Pat. Nos. 4,439,520; 4,414,310; 4,433,048; 4,643,966; 4,647,528; 4,665,012; 4,672,027; 4,678,745; 4,693,964; 4,713,320; 4,722,886; 4,755,456; 4,775,617; 4,797,354; 4,801,522; 4,806,461; 4,835,095; 4,853,322; 4,914,014; 4,962,015; 4,985,350; 5,061,069 and 5,061,616.
The silver halide grains to be used in the invention may be prepared according to methods known in the art, such as those described in Research Disclosure I and James, The Theory of the Photographic Process. These include methods such as ammoniacal emulsion making, neutral or acid emulsion making, and others known in the art. These methods generally involve mixing a water soluble silver salt with a water soluble halide salt in the presence of a protective colloid, and controlling the temperature, pAg, pH values, etc, at suitable values during formation of the silver halide by precipitation.
The silver halide to be used in the invention may be advantageously subjected to chemical sensitization with compounds such as gold sensitizers (e.g., aurous sulfide) and others known in the art. Compounds and techniques useful for chemical sensitization of silver halide are known in the art and described in Research Disclosure I and the references cited therein.
The photographic elements of the present invention, as is typical, provide the silver halide in the form of an emulsion. Photographic emulsions generally include a vehicle for coating the emulsion as a layer of a photographic element. Useful vehicles include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives (e.g., cellulose esters), gelatin (e.g., alkali-treated gelatin such as cattle bone or hide gelatin, or acid treated gelatin such as pigskin gelatin), gelatin derivatives (e.g., acetylated gelatin, phthalated gelatin, and the like), and others as described in Research Disclosure I. Also useful as vehicles or vehicle extenders are hydrophilic water-permeable colloids. These include synthetic polymeric peptizers, carriers, and/or binders such as poly(vinyl alcohol), poly(vinyl lactams), acrylamide polymers, polyvinyl acetals, polymers of alkyl and sulfoalkyl acrylates and methacrylates, hydrolyzed polyvinyl acetates, polyamides, polyvinyl pyridine, methacrylamide copolymers, and the like, as described in Research Disclosure I. The vehicle can be present in the emulsion in any amount useful in photographic emulsions. The emulsion can also include any of the addenda known to be useful in photographic emulsions. These include chemical sensitizers, such as active gelatin, sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium, phosphorous, or combinations thereof. Chemical sensitization is generally carried out at pAg levels of from 5 to 10, pH levels of from 5 to 8, and temperatures of from 30 to 80xc2x0 C., as illustrated in Research Disclosure, June 1975, item 13452 and U.S. Pat. No. 3,772,031.
The silver halide may be sensitized by sensitizing dyes by any method known in the art, such as described in Research Disclosure I. The dye may be added to an emulsion of the silver halide grains and a hydrophilic colloid at any time prior to (e.g., during or after chemical sensitization) or simultaneous with the coating of the emulsion on a photographic element. The dye/silver halide emulsion may be mixed with a dispersion of color image-forming coupler immediately before coating or in advance of coating (for example, 2 hours).
Photographic elements of the present invention may also usefully include a magnetic recording material as described in Research Disclosure, Item 34390, November 1992.
Photographic elements of the present invention are preferably imagewise exposed using any of the known techniques, including those described in Research Disclosure I, section XVIII.
Photographic elements comprising the composition of the invention can be processed in any of a number of well-known photographic processes utilizing any of a number of well-known processing compositions, described, for example, in Research Disclosure I, or in James, The Theory of the Photographic Process 4th, 1977. In the case of processing a reversal color element, the element is first treated with a black and white developer followed by treatment with a color developer.
As mentioned above, the 1-aryl-4-aryloxy-2-pyrazolin-5-one coupler plus sulfide, sulfoxide or sulfone combinations of this invention may be used together with a variety of other types of couplers in the same layer or in different layers of a multilayer photographic material. Specifically contemplated is the use of the coupler plus sulfur compound combinations of this invention in one or more green-sensitive layers of a photographic material containing one or more pyrazoloazole couplers or one or more 1-phenyl-3-anilino-2pyrazolin-5-one couplers with thiophenol coupling-off groups.
As to the synthesis of the above described 1-aryl-4-aryloxy-2pyrazolin-5-one magenta couplers, the synthesis of aryloxypyrazolones where R2 in the above formulae is acylamino or anilino can be found in U.S. Pat. Nos. 3,419,391; 3,519,429 and 4,692,529. In addition, 4,692,529 and DE 4 040 472 A1 describe the synthesis of such compounds. U.S. Pat. No. 3,419,391 describes the synthesis of aryloxypyrazolones where R2 in the above formulae is an alkyl. Another synthesis for the above described 1-aryl-4-aryloxy-2pyrazolin-5-one magenta couplers which is more generally applicable, is described below in relation to the synthesis of A4.
Example of Synthesis: Compound A4
Preparation of t-butyl ethyl bromomalonate
t-Butyl ethyl malonate (25.00 g, 0.13 mol) was dissolved in toluene and warmed to 80xc2x0 C. To the resulting solution was added 1,3-dibromo-5,5-dimethylhydantoin (25.00 g, 0.07 mol). The reaction was stirred at elevated (80xc2x0 C.) temperature 18 h. The reaction was cooled concentrated and taken up in Et2O. The organic layer was washed, with sat. NaHCO3 (2xc3x97), brine (3xc3x97), dried (MgSO4), filtered and concentrated. Purification by filtration on silica (70:30; hept:EtOAc) yielded 33.0 g (93%) of a light yellow oil. NMR and MS indicated a mixture of three compounds SM (20%), monobrominated (55%) and dibromonated diesters (25%). The material was used without further purification.
Preparation of t-butyl ethyl-2(p-nitrophenoxy) malonate
p-Nitrophenol (3.58 g, 26 mmol) was flushed with N2 and dissolved in dry THF (100 ml). To the resulting solution was added potassium t-butoxide (2.52 g, 22 mmol). The resulting orange solution was stirred for 15 min. and a solution of t-butylethyl bromomalonate (5.89 g, 0.022 mol) in dry THF (20 ml) added dropwise. The reaction was stirred at room temperature for 4 h and concentrated. The residue was taken up in Et2O and the organic layer washed with H2O (1x), sat. NaHCO3 (4x), brine (3x), dried (MgSO4), filtered and concentrated. The resulting solid was stirred in heptane, filtered (2x) to remove t-butyl ethyl malonate contaminate and concentrated. The solid was dissolved in EtOAc (100 ml) and an aqueous solution of sodium dithionite (100 ml; Na2S2O4 125 g/1) added. The two phase solution is stirred 18 h. The phases are separated and the organic phase washed with H2O (2x), brine (2x), dried (MgSO4), filtered and concentrated. The resulting off white solid 6.35 g (88%) is used without further purification.
Preparation of ethyl- (D-nitrophenyloxy)-malonate magnesium salt
t-Butyl ethyl-2(p-nitrophenyloxy) malonate (37.2 g, 0.11 mol) was dissolved in CH2Cl2 (400 ml) and trifluoroacetic acid (100 ml) added. The reaction was stirred for 2 h and taken up in CH2Cl2. The solution was washed with H2O (3xc3x97), brine (2xc3x97), dried (MgSO4), filtered and concentrated (bath temp  less than 45xc2x0 C.). The resulting oil was purified on silica gel (60A; 230-400 mesh; 70:30; hept:EtOAc then acetone) yielding 27.1 g (88%) of a white solid. The white solid was flushed with N2 and dissolved in dry THF (250 ml). To the resulting solution was added Mg(OEt)2 (5.33 g, 0.046 mol). The solution was stirred 18 h at room temperature and concentrated (bath temp  less than 45xc2x0 C.). The resulting foam was twice diluted with dry cyclohexane (xcx9c50 ml) and concentrated. The solid was dried under high vacuum to a free flowing off-white solid. The material was used without further purification.
Preparation of Ethyl-2(i-nitrophenyloxy)-3-oxohexadecanoate
Carbonyldiimidazole (16.7 g, 104 mmol) was flushed with N2 and dissolved in dry THF (500 ml). To the resulting solution was added a solution of myrisitic acid (21.5 g, 94 mmol) in dry THF (50 ml). The reaction was stirred two hours at room temperature, then ethyl-(p-nitrophenyloxy)-malonate magnesium salt (25.0 g, 44 mmol) was added in portions over 5 minutes. The reaction is stirred at room temperature 18 h and quenched with NH4Cl. The solution is concentrated and taken up in Et2O. The organic layer is washed with, 1M HCl (1xc3x97), H2)(2xc3x97), sat. NaHCO3 (2xc3x97), brine (2xc3x97), dried (MgSO4), filtered and concentrated. Purification on Silica (60A; 230-400 mesh; 80:20; hept:EtOAc) yielded 22.2 g (60%) of a light yellow oil.
Preparation of 1-(2,4,6-trichlorophenyl)-3-tridecyl-4-(4-nitrophenoxy)-5-pivaloyl pyrazole
Ethyl-2(p-nitrophenyloxy)-3-p -nitrophenyloxy)-3oxohexadecanoate (19.5 g, 45 mmol) was flushed with N2 and dry MeOH (50 ml) added. Approximately 10 ml THF was added to improve solubility. Trichlorophenylhydrazine (10.4 g, 49 mmol) was added followed by HCl(g) (until the reaction mixture was homogenous ca.35 sec). The reaction was stirred for 18 h, diluted with Et2O (200 ml) and filtered. The resulting solution was washed with H2O (2xc3x97), sat. NaHCO3 (2xc3x97), brine (2xc3x97), dried (MgSO4), filtered and concentrated. The resulting oil was flushed with N2 and dissolved in CH2Cl2. Pivaloyl chloride (11 ml, 91 mmol) was added and followed by N,N-dimethylaminopyridine (cat. 0.4 g). The solution was stirred 10 min. then a solution of Et3N (14 ml, 100 mmol) in CH2Cl2 was added dropwise. The resulting black solution was stirred 1 h. and taken up in CH2Cl2. The organic portion was washed with 0.5M HCl (2xc3x97), H2O (2xc3x97), sat. NaHCO3 (2xc3x97), brine (2xc3x97), dried (MgSO4), filtered and concentrated. Purification on silica (60A; 230-400 mesh; 90:10; hept:EtOAc) yielded 7.4 g (25%) of a white solid.
Preparation of A4
1-(2,4,6-trichorophenyl)-3-tridecyl-4-(4-nitrophenoxy)-5-pivaloyl pyrazole (7.4 g, 11 mmol) was flushed with N2 and dissolved in THF (5 ml) and dry MeOH (40 ml). K2CO3 (3.1 g, 22 mmol) was added and the reaction stirred at room temperature for 1 h. The resulting solution was taken up in Et2O and the organic portion washed with 0.5M HCl (2xc3x97), sat. NaHCO3 (2xc3x97), Na2S2O4 (125 g/1) (2xc3x97), brine (2xc3x97), dried (MgSO4), filtered and concentrated yielding 5.9 g (93%) of a white solid.

Photographic elements containing aryloxypyrazolone couplers and sulfur containing stabilizers

Abstract: Where R1, R2, R3, n, R8 and R9 are defined in the specification.


The occurrence of reception errors due to failure to discriminate between a new transmission and a retransmission is reduced by a wireless communication comprising a storage unit operable to store received data; and a decoding unit operable to obtain a first decoding result by decoding new received data, which is not combined with the stored received data, and which obtains a second decoding result by decoding the new received data, which is combined with the stored received data.

1. Field of the Invention
The present invention relates to a wireless communication device and mobile station, and in particular to a system using wireless communication devices and mobile stations is the W-CDMA (UMTS) mobile communication system.
2. Description of the Related Art
Standardization is currently progressing within the 3GPP (3rd Generation Partnership Project) on the W-CDMA (UMTS) scheme, one scheme for a third generation mobile communication systems. HSDPA (High Speed Downlink Packet Access), which provides a maximum transmission speed of approximately 14 Mbps, has been specified as one theme of the standardization.
HSDPA is characterized in that it employs an adaptive coding modulation scheme, for example, switching adaptively between a QPSK modulation scheme and a 16-QAM scheme depending on the wireless environment between the base station and mobile station.
HSDPA furthermore employs an H-ARQ (Hybrid Automatic Repeat reQuest) scheme. Under H-ARQ, when a mobile station detects an error in the data received from the base station, a retransmission request is made from the mobile station to the base station, and the data is retransmitted from the base station. The mobile station then performs error correction decoding using both the already received data and the retransmitted received data. Thus, H-ARQ increases the benefits of error correction decoding and reduces the number of retransmissions by effectively using already received data.
The main wireless channels used in HSDPA include HS-SCCH (High Speed-Shared Control Channel), HS-PDSCH (High Speed-Physical Downlink Shared Channel) and HS-DPCCH (High Speed-Dedicated Physical Control Channel).
HS-SCCH and HS-PDSCH are both downlink (i.e., in the direction from the base station to the mobile station) common channels; HS-SCCH is a control channel for transmitting various parameters relating to the data transmitted on HS-PDSCH. The various parameters include, for instance, modulation type information indicating what modulation scheme is to be used for transmitting data on HS-PDSCH, spreading code assignment numbers (code numbers), information on the pattern of rate matching performed on the transmitted data, and the like.
HS-DPCCH, on the other hand, is a dedicated uplink control channel, in the direction from the mobile station to the base station; it is used by a mobile station to transmit ACK and NACK signals, depending on whether the data received via HS-PDSCH was received properly or not. If the mobile station failed to receive data (when the received data has a CRC error or the like), a NACK signal would be transmitted from the mobile station to the base station, whereupon the base station would execute retransmission control.
The HS-DPCCH is also used by the mobile station to periodically transmit to the base station the results of determination of the reception quality (e.g., SIR) of the signal received from the base station as a CQI (Channel Quality Indicator). The base station evaluates the goodness of the downlink wireless environment based on the received CQIs, and switches for instance to a modulation scheme that allows data to be transmitted at higher speeds if the environment is good. If the wireless environment is not good, the base station adaptively switches to a modulation scheme whereby data is transmitted at lower speed, etc.
Channel Structure
Next, the channel arrangement involved in HSDPA will be explained.
FIG. 1 is a diagram illustrating the channel arrangement involved in HSDPA. Since W-CDMA employs a code division multiplexing scheme, each channel is separated by means of a code.
First, the channels which have not been explained will be briefly described.
CPICH (Common Pilot Channel) and P-CCPCH (Primary Common Control Physical Channel) are respectively downlink common channels.
CPICH is a channel used by the mobile station as a timing reference for channel estimation, cell search and other downlink physical channels within the same cell; it is a channel used to transmit the so-called pilot signal. P-CCPCH is a channel for transmitting broadcast information.
Next, the timing relationship of the various channels will be described.
As shown in FIG. 1, each channel comprises one frame (10 ms) of 15 slots. As explained earlier, CPICH is used as a reference for other channels, so the head of the frame of P-CCPCH and HS-SCCH is aligned with the head of the CPICH frame. Here, the head of the HS-PDSCH frame is delayed by two slots relative to HS-SCCH and the like. This is in order to provide advance notice, via the HS-SCCH, of the demodulation type information and spreading code information which the mobile station needs in order to perform demodulation of the HS-PDSCH. Therefore, the mobile station selects the appropriate demodulation scheme and despreading code according to the information provided in advance on HS-SCCH to execute the processing of HS-PDSCH demodulation, etc.
Furthermore, HS-SCCH and HS-PDSCH comprise subframes of three slots.
The above was a simple description of the HSDPA channel arrangement.
Next, the content and coding procedure of the data transmitted on HS-SCCH will be described.
Data Transmitted on HS-SCCH
The following data are transmitted on HS-SCCH. Each datum is used for reception processing of HS-PDSCH, on which transmission takes place with a two slot delay.
(1) Xccs (Channelization Code Set information)
(2) Xms (Modulation Scheme information)
(3) Xtbs (Transport Block Size information)
(4) Xhap (Hybrid ARQ Process information)
(5) Xrv (Redundancy and constellation Version)
(6) Xnd (New Data indicator)
(7) Xue (User Equipment identity)
(1) through (7) will be described.
(1), Xccs, is a datum indicating the spreading code used for transmitting data on HS-PDSCH (e.g., a datum indicating a combination of multicode number and code offset), and consists of 7 bits.
(2), Xms, is a datum indicating whether the modulation scheme used on HS-PDSCH is QPSK or 16-QAM, and consists of 1 bit.
(3), Xtbs, is a datum used for computing the transport block size of the data transmitted on HS-PDSCH (the size of the data transmitted in one subframe of HS-PDSCH), and consists of 6 bits.
(4), Xhap, is a datum indicating the H-ARQ process number, and consists of 3 bits. A base station basically cannot determine whether or not a mobile station was able to receive data until the base station receives an ACK or NACK. However, if it were to wait until the ACK or NACK was received before transmitting a new data block, the transmission efficiency would decrease. Thus, in order to enable transmission of new data blocks before receiving an ACK or NACK, a process number is defined for each data block transmitted in subframes, and the mobile station is made to perform reception processing in pieces based on the process number. Namely, under the condition that the base station will assign the same process number when performing retransmission as the process number assigned to the previously sent transport block, each transport block is given the corresponding process number, which is transmitted in advance via HS-SCCH as the Xhap.
Therefore, the mobile station classifies data received via the HS-PDSCH based on the received Xhap, and performs discrimination of new transmission or retransmission based on Xnd, which will be described below, in the stream of data for which the same process number was indicated via HS-SCCH, as well as combining new data and resent data, etc. (H-ARQ processing, etc.).
(5), Xrv, is a datum which indicates the redundancy version (RV) parameter (s, r) and constellation version parameter (b) for HS-PDSCH retransmission, and consists of 3 bits.
For Xrv, there is a first technique (Incremental Redundancy) whereby the parameters are updated for new transmission and retransmission, and a second technique (Chase Combining) whereby the parameters are not changed for new transmission or retransmission.
In the first technique, the puncture pattern and the like varies, so the bits to be transmitted change between new transmission and retransmission, while in the second technique, they do not change.
(6), Xnd, is a datum indicating whether a block transmitted on HS-PDSCH is a new block or a resent block, and consists of one bit. For example, when transmitting a new block, it would be switched from 0 to 1 or from 1 to 0, while when retransmitting, the same value would be used as before, without switching.
For example, when performing a sequence of new transmission, retransmission, new transmission, retransmission, retransmission; new transmission, the Xnd would change in the order 1, 1, 0, 0, 0, 1.
(7), Xue, is a datum indicating the identification information of the mobile station, and consists of 16 bits.
FIG. 2 is the structure of the HS-SCCH coding unit.
In FIG. 2, 1 is a coding unit, 2 is a rate matching unit, 3 is a multiplication unit, 4 is a CRC computation unit, 5 is a multiplication unit, 6 is a coding unit, 7 is a rate matching unit, 8 is a coding unit, and 9 is a rate matching unit.
The operation of each block will be described next.
(1) Xccs (x1,1-x1,7), represented in 7 bits, and (2) Xms (x1,8), represented in 1 bit, are inputted into the coding unit 1 as a datum with a total of 8 bits. Here, the first half of the subscript signifies that this relates to data transmitted in the first slot, while the number of the second half, separated by a comma (,), signifies the number of the bit.
Now, the coding unit 1 appends 8 tail bits to the inputted data, and performs convolutional coding at a code rate of 1/3 on a total of 16 bits. Thus, the encoded data becomes a total of 48 bits, and is given to the rate matching unit 2 as z1,1-z1,48. The rate matching unit 2 performs puncturing, repetition, etc. of specific bits, and outputs the bits adjusted to the number of bits (assumed to 40 here) that will fit into the first slot (r1, 1-r1,40).
Data from the rate matching unit 2 are multiplied by c1-c40 in the multiplication unit 3 and outputted as s1,1-s1,40, and are transmitted in the first slot (first part) of HS-SCCH in FIG. 1, which is the slot at the head of a subframe.
Here, c1-c40 are obtained by adding 8 tail bits to the data from (7) Xue (Xue1-Xue16) and then convolutionally encoding, in coding unit 8, it at a coding rate of 1/2 to obtain b1-b48, which are further subjected, in rate matching unit 9, to the same bit adjustment as in the rate matching unit 2.
Furthermore, the 6-bit (3) Xtbs (x2,1-x2,6), 3-bit (4) Xhap (x2,7-x2,9), 3-bit (5) Xrv (x2,10-x2,12) and 1-bit (6) Xnd (x2, 13), are inputted as a total of 13 bits y2,1-y2,13, with the 16 bits y2,14-y2,29 further added for a total of 29 bits, y2,1-y2,29, into the coding unit 6.
Here, y2,14-y2,29 are obtained by performing CRC computation on the total of 21 bits of (1) through (6) in the CRC computation unit 4, and multiplying the results of that computation, c1-c16, by (7) Xue (xue1-xue16).
The y2,1-y2,29 inputted into the coding unit 6 have 8 tail bits added thereto and are convolutionally encoded at a coding rate of 1/3 and inputted as 111 bits, x2,1-z2,111, into the rate matching unit 7.
The rate matching unit 7 outputs 80 bits, r2,1-r2,80 by means of processing such as the aforementioned puncturing, and these r2,1-r2,80 are transmitted in the second and third slot (second part) of the one subframe on HS-SCCH in FIG. 1.
As described above, the data of (1) and (2) are transmitted in a first part, while (3) through (6) are transmitted in a second part, thus being transmitted in distinctly in separate slots, but these data are subjected to a common CRC computation, with the CRC computation result being transmitted in the second part, so detection of reception error becomes possible once both the first and second part are completely received.
Furthermore, since the data transmitted in the first slot is multiplied by (7) Xue in the multiplication unit 3 after undergoing convolutional coding by the coding unit 1, when data addressed to another station is received in the first slot, the likelihood generated in the decoding process will be smaller compared to if it were addressed to this station, so a comparison of the likelihood to a reference value can reveal that the possibility of it not being addressed to this station is high.
Coding of Data Transmitted on HS-PDSCH
Next, the process leading to transmission of data via HS-PDSCH will be described using a block diagram.
FIG. 3 is a diagram which illustrates a transmission device according to the present invention.
The transmission device (wireless base station) of a W-CDMA communication system compatible with the above-described HSDPA will be described as an example transmission device. This can also be applied to transmission devices in other communication systems.
In the drawing, 10 represents a control unit which sequentially outputs the transport data (the data transmitted within one subframe) to be transmitted via HS-PDSCH, as well as controlling the various units (11 through 26, etc.). The values of (1) through (7) described in FIG. 2 are assigned by this control unit 10.
Since HS-PDSCH is a shared channel, it is allowed for successively outputted data to be addressed to different mobile stations.
11 represents a CRC attachment unit which performs a CRC computation on the successively inputted transport data (data transmitted within the same wireless frame) and attaches the CRC computation result to the tail of this transport data, and 12 represents bit scrambling unit which scrambles the transport data with the CRC computation result attached thereto in bit units to impart randomness to the transmitted data.
13 represents a code-block segmentation unit which segments (e.g., into two equal parts) the inputted bit-scrambled transport data when it exceeds a certain data length, in order to prevent increase in computational volume of the receiving side decoder due to excessive length of the data to be encoded in the following channel coding, and the like. The drawing illustrates output in a case where the inputted data length exceeded a certain data length and was divided into two equal parts (segmented into a first data block and second data block). Of course, cases where the number of segments is other than two are also possible, as are cases where the data is divided not into equal parts but into different data lengths.
14 represents a channel coding (encoding) unit which performs error correction coding separately on each segmented datum. Here, it is assumed that a turbo coder is used for the channel coding unit 14.
Therefore, the first output of the channel coding unit, for the first block, contains: the important systematic bits (U), which are the same data as the data to be coded; the first redundancy bits (U′) obtained by convolutionally coding the systematic bits (U); and the second redundancy bits (U″) obtained by interleaving the systematic bits and then convolutionally coding in the same manner. Likewise, the second output contains the systematic bits (U), first redundancy bits (U′) and second redundancy bits (U″) for the second block.
15 represents a bit separation unit which separates the first block and second block, serially inputted from the channel coding unit 14 (turbo coder), into the systemic bits (U), first redundancy bits (U′) and second redundancy bits (U″), and outputs them.
16 represents a first rate matching unit which performs rate matching, e.g. puncturing, on the input data (the data of all separated blocks when separated into multiple blocks) in order to make it fit into a specific region of the following virtual buffer unit 17.
17 represents a virtual buffer unit, in which a region is set by the control unit 10 in accordance with the reception processing capacity of the mobile station to be transmitted to, and which stores data rate-matched by the first rate matching unit 16 in that region. During retransmission, the processing from the CRC attachment unit to the first rate matching unit can be omitted by outputting the stored data, but when one wishes to change the coding rate during retransmission, etc., it is preferable not to use the stored data but rather to re-output the transmission data held by the control unit. It is also possible to not provide an actual buffer for the virtual buffer unit 17 and to have the data pass through directly. In this case, resent data would be re-outputted from the control unit 10.
18 represents a second rate matching unit for adjusting the data length with control unit 10 to one that can fit inside the designated subframe; it adjusts the data length of the inputted data to the designated data length by performing puncturing and repetition on it.
This second rate matching unit 18 performs rate matching according to the previously described RV parameter.
Namely, according to the RV parameter, when s=1, rate matching is carried out so as to leave as many systematic bits as possible; on the other hand, when s=0, it is permitted for the systematic bits to be reduced and for more redundancy bits to remain. Furthermore, rate matching and puncturing are performed based on a pattern according to r.
19 represents a bit collection unit which arranged the data from the second rate matching unit 19 into a plurality of bit sequences. Namely, the data of the first block and the data of the second block are arranged according to a specific bit arrangement method to output a plurality of bit sequences serving to indicate the signal points on a phase plane. Since the 16-QAM modulation scheme is used in this example, the bit sequence consists of four bits; when using a 64-QAM modulation scheme, the bit sequence would be made six bits, and when using a QPSK modulation scheme, the bit sequence would be made two bits.
20 segments and outputs bit sequences into the same number of systems as the number of the spreading code (code number) provided by the control unit 10. Namely, it represents a physical channel segmentation unit which, when the code number in the transmission parameters provided by the control unit 10 is N, maps the inputted bits sequentially to 1 through N systems and outputs them.
21 is an interleaving unit which performs interleaving on the bit sequences of N systems and outputs them.
22 is a constellation rearrangement unit for 16-QAM, which is able to rearrange bits within, each inputted bit sequence. Bit rearrangement is carried out according to the earlier described constellation version. Examples of bit rearrangement include substituting high order and low order bits; it is preferable for bit substitution to be carried out by the same rule for multiple bit sequences.
23 is a physical channel mapping unit which maps the bit sequences of N systems to the corresponding spreading section of the following spreading unit 24.
24 is a spreading unit which comprises a plurality of spreading sections, each of which outputs the corresponding I and Q voltage based on each bit sequence of N systems, performing spreading with a different spreading code in each case and outputting the result.
25 represents a modulating unit which combines the signals spread by the spreading unit 24, and based thereon, performs amplitude phase modulation, for instance by the 16-QAM modulation scheme, amplifies by means of a variable gain amplifier, performs frequency conversion to a wireless signal, and then outputs the wireless signal to the antenna to enable transmission.
Since. HSDPA allows multiplexing of signals addressed to other mobile stations by means of spreading codes in subframes of the same timing, it is preferably to provide multiple sets of 10 through 25 and of the variable gain amplifier, etc. (which will be referred to as transmission sets), and to combine the output signals of the variable gain amplifiers, then frequency-convert them in common, and then transmit the result to the antenna. Of course, since separation by code is necessary, the spreading code used by the spreading unit 24 of each transmission set would differ so as to allow separation.
26 represents a reception unit, which receives signals from a mobile station received via HS-DPCCH or the like, and provides the ACK or NACK signal, CQI, etc. to the control unit 10.
As described above, when an ACK signal is received, the next new data is transmitted, while in the case of a NACK signal or if there is no response within a specific period of time, the control unit 10 performs retransmission control to retransmit the transmitted data. Retransmission is limited to a set maximum number of retransmissions; if the maximum number of retransmission is reached without receiving an ACK signal from the mobile station, the control unit 10 provides control to switch to transmission of the next new data.
In cases where no maximum number of retransmission is defined, it is also possible to start a timer from a new transmission, and switch to transmission of the next new data if a specific time is detected to have elapsed with no ACK signal having been received.
The foregoing was a description of the designations and operation of each unit.
Matters relating to the above-described HSDPA are disclosed for instance in 3rd Generation Partnership Project: Technical Specification Group Radio Access Network; Multiplexing and channel coding (FDD) (3G TS 25.212) and 3rd Generation Partnership Project: Technical Specification Group Radio Access Network; Physical layer procedures (FDD) (3G TS 25.214).
According to the background art described above, by means of the data (Xnd) for discriminating between new transmission and retransmission, a wireless communication device is able to determine whether received data (HS-PDSCH) is a new transmission or retransmission, but errors may occur in this data (Xnd), and being unable to detect a change in Xnd, the next change in Xnd may be erroneously taken to indicate a retransmission.
In particular in the case of a wireless communication device which combines already received data with retransmitted data, if it cannot correctly discriminate between new transmission and retransmission, it will end up making an incorrect combination, leading to a reception error.
Therefore, a need arises to reduce the occurrence of reception errors.

Wireless communication device and mobile station


A method of manufacturing a plurality of molded components including (a) providing a carrier to a manufacturing assembly; (b) forming the molded components on the carrier, the molded components having a sacrificial portion secured to the carrier and being movable along the carrier, and a functional portion extending from the sacrificial portion, adjacent sacrificial portions are spaced from one another by a first distance; (c) winding the carrier in a forward direction onto the uptake device; and (d) unwinding the uptake device in a reverse direction such that the carrier and molded components move toward the source device, one of the molded components contacts the latch preventing the molded components from moving in the reverse direction such that adjacent sacrificial portions are moved closer together to a second distance that is less than the first distance.

Molded components, particularly micro-molded components, present challenges that arise in the context of transporting, storing, feeding and handling such components through manufacturing systems. These challenges are particularly associated with the difficulty of gripping and securing these components due to their small size and the force of static electricity, which makes the components stick to production equipment, i.e., to storage trays and/or magazines, or even to one another.
The electronics industry uses plastic and metal component carriers quite frequently. For example, U.S. Pat. No. 5,148,596 describes a continuous molded electronic component assembly process in which a continuous line of components is supplied on reels for assembly and insertion. U.S. Pat. No. 6,003,676 describes a carrier tape formed with a plurality of product receiving pockets molded thereon. U.S. Pat. No. 7,134,197 describes a method such that plastic parts can be transported on a carrier for manufacturing of a final product based initially on the plastic part.
However, there still exists a need to provide molded components and a method that overcomes the above-mentioned problems associated with transporting, storing, feeding and handling molded components.

Method of manufacturing a plurality of molded components


The present invention relates to a method of manufacturing a brush head comprising a brush head body carrying bristle bundles, in particular for tooth brushes, by way of injection molding, in which a first plastic component is injected into a first mold cavity for forming a bristle carrier, and ends of bristle filaments projecting into the first mold cavity are encompassed by the first plastic component. In order to guarantee a complete filling of the mold and a favorable reproduction of the mold cavity geometry, but to avoid at the same time a penetration of plastic mass into ducts in which the bristle filaments are held, it is suggested by the present invention that the bristle carrier manufactured during the first step is relocated into another mold cavity, which is larger than the bristle carrier, and which is filled with a hard component. The present invention further relates to a brush head, in particular for a tooth brush, comprising at least one brush head body carrying a bristle bundle in which the fixing-sided ends of bristle filaments are embedded by an over-molding, wherein it is suggested according to the invention in order to provide a brush head complying with the above-mentioned demands, that the brush body comprises a bristle carrier encompassing the bristle filaments on the attachment side, the bristle carrier being embedded into a hard component.

1. Field of the Invention
The present invention refers to a method of manufacturing a brush head, in particular for tooth brushes, comprising at least one brush head carrier carrying bristle filaments, by way of an injection molding process, in which a first plastic component is injected into a first mold cavity for forming a bristle carrier, and in which ends of bristle filaments projecting into the first mold cavity are encompassed by the first plastic component. The present invention relates further to a brush head, in particular for a tooth brush, comprising a brush head body carrying brush filaments, in which the fixing-sided ends of bristle filaments are embedded by means of over-molding.
2. Description of the Prior Art
A method of the above-mentioned type is for instance known from DE 845 933 going back to the applicant. The generic method differs from the conventional method of manufacturing a brush head in which recesses are made in the brush head when the brush head is injection molded, wherein bristle filaments are inserted and held into the brush head later by means of anchors, in such a manner that the bristle filaments are joined with the brush head body directly during the injection molding process. In order to obtain as reliable a connection as possible between the brush head body and the bristle filaments usually combined to form bristle bundles, the bristle bundles are regularly melted to a unit at their fixing-sided ends before injecting the plastic component. In the generic process, the enlargement and/or the fixing-sided ends of the bristle filaments are fully or partially encompassed by the first plastic component.
The generic method is particularly suitable for the manufacture of brushes having a relatively thin brush head and this is also preferable for cost reasons. However, the sealing of the ducts of the injection molding tool in which the bristle bundles are held is problematic. In view of an optimal mold filling and a precise design of the mold cavity geometry, as high an injection molding pressure as possible is preferred. The ducts holding the bristle bundles, however, form outlets into which plastic mass is pressed where excessive injection pressure is applied. Thereby the bundle position of the bristle bundles is damaged. The brush is useless. When excessive injection pressure is applied the bundles are also pressed out of the ducts.
Suggestions as to how to solve this problem were not missing in the prior art. It is suggested by DE 38 52 520 that sleeves be inserted into the ducts that have slots at their mold cavity-sided ends and which abut at a conical surface of the injection molding tool and which are pressed radially inward in such a manner to seal the bristle bundle held in the sleeve. It is also known from DE 15 54 925 to hold the bristle bundles in a clamping plate to seal the mold cavity with respect to the bristle bundles in case of injection molding pressure. The proposed solution does, however, require an expensive construction. The solution mentioned last moreover can only be realized in ducts that are arranged in an offset manner to one another. Thereby the geometry of the bristle field is predefined and restricted in an undesired manner.
Moreover, it is known from the prior art to attach the enlargement formed by melting at lie the fixing-sided ends of the bristle bundle directly to the mouth of the ducts holding the bristle bundles (DE 35 11 528). The bundles are held in the brush head body during such a process only with an insufficient expansion force. This should be avoided by an extension of the ducts into the mold cavity as suggested by DE 36 42 124. However, ducts projecting from the bristle surface into the brush body encompassing the individual bristle bundles are produced in which bacteria and dirt can get caught, which is not tolerable in particular in body care brushes, especially tooth brushes.
Besides constructive measures of sealing a mold cavity, it is furthermore known from the prior art to adapt the procedure and to let a relatively low injection pressure act when injecting the plastic mass, said injection pressure being increased after stabilizing the surface of the brush head body penetrated by the bristle bundles in order to counteract a thermal loss and to achieve as complete a design of the mold geometry as possible. Constructive measures at the mold cavity geometry were suggested which should enhance a possibly early stabilization of the surface of the brush head body penetrated by the bristle bundles.
It was for instance suggested in EP 0 749 711 that a collar be formed at the injection molding tool, said collar projecting inwardly into the mold cavity, said collar encompassing each individual bristle bundle. This proposal involves hygiene problems, since this collar is formed at the ready brush as an annular gap encompassing the bristle bundles in which dust and impurities can get caught. According to a further proposal of EP 0 759 711, the shaping tool shall have an annular gap encompassing each bristle bundle to enhance the quick stabilization of shaping mass encompassing the respective bristle bundle. This measure also leads to a contoured, i.e. unplanar, bristle surface. The bristle surface is the surface of the brush head body penetrated by the bristle bundles.
The suggestions discussed above by means of which an emerging of plastic mass from the ducts when over-molding the fixing-sided bristle bundle is prevented, were not capable of fully eliminating the underlying problem. Where injection molding pressure is low at least at the beginning of the filling of the mold, the mold cavity geometry is not formed with the necessary precision If the injection molding pressure is increased, additional sealing measures are required to prevent a penetration of plastic mass into the ducts which hold the bristle bundles. Moreover, the generic method is regularly performed by easily flowing polypropylene having a high melding index (MFI) and which can be easily processed at relatively low injection molding pressures of e.g. 10 to 15 bar at a quite favorable mold filling.
Many brushes, in particular tooth brushes as well as the brush head bodies of these tooth brushes shall, however, be manufactured of plastics having difficult flow properties, which can only be introduced into the mold cavity at relatively high injection pressures of several hundred bar. The use of such high-quality plastics is, up to the present day, restricted to such brush heads at which the brush body is first of all formed by means of injection molding and is subsequently provided with bristle bundles which are fixed in the brush head body by means of metal anchors.
The present invention is s n the object of solving the above-mentioned problems and of developing a method of manufacturing a brush head of the above-mentioned kind in a manner that a brush head body or a complete tooth brush body containing the brush head body can be manufactured with a perfect surface and a precise design of the mold cavity geometry without the risk of plastic mass penetrating into the ducts holding the bristle bundles and the risk of damaging the bristle filaments projecting over the brush head body. The present invention is furthermore based on the object of providing a brush head of a tooth brush body containing the brush head body complying with these demands.
To achieve the above-mentioned object, the generic method is developed by the invention on file in that the bristle carrier is located into another mold cavity to form the brush head body, said mold cavity being larger than the bristle carrier and which is filled by a hard component. In the method according to the invention, the brush head body is manufactured by means of a two-component or two-color or multi-component injection molding process. During the first step of the two-component injection molding process, an easily flowing plastic material, which preferably has a low pastificabon temperature, is filled into the first mold cavity. This first plastic component in particular can be an easily flowing plastic material that can be processed at low temperatures and that has a high melting index (MFI). The first plastic component is only selected in view of the fact that a sufficient mold filling at the lowest possible temperatures and the lowest pressures possible. A complete filling of the mold cavity is not required, since preferably at most the surface of the core of the brush head body formed of the first component is visible at the surface thereof A plastic component having a relatively low plastification temperature is in particular chosen in view of the thermal affect of the bristle filaments projecting into the first mold cavity. Since the re-erection ability of these bristle filaments is ensured by hidden stabilized molecule chains, a heating of the stabilized molecules and therefore an at least partial reorientation of the molecules should be fully prevented, if possible.
There are no restrictions regarding the selection of the material and the injection molding parameters for processing the second components. The bristle filaments are held in the bristle carrier formed by the first plastic component. This bristle carrier seals the duds of the second mold cavity holding the bristle filaments. High injection pressures can therefore not reach the mouth of the ducts and cannot lead to a high pressing-out of the second plastic component into the ducts. High-quality or transparent plastics with difficult flow properties, such as ABS (acrylonitrile-butadiene-styrene copolymer), CAP (cellulose acetopropdonate), CA (acetyl cellulose), PET (polyethylene terephtalate), POM (polyaformaldeyde) and PA (polyamide) can be used for forming the brush head body without having to forsake the advantages of an anchor-less attachment of the bundle in the brush head.
Due to the sealing of the ducts by the bristle carrier and the embedding of the bristle bodies into same, the injection of the second or a further plastic component into the second mold cavity is not subject to restrictions regarding the injection pressure, the selection of the materials or the injection temperature of the plastics. By filling the further mold cavity by the hard component, the bristle carrier formed first is over-molded. During this over-molding process, the bristle carrier may almost be completely embedded into the hard component. Then, almost the entire surface of the brush head body or a brush containing the brush head body is almost exclusively formed by the hard component. The bristle carrier can be joined with the hard component in the further mold cavity only on one side possibly by interposition of one or a plurality of further components, preferably a soft-elastic component. There, the brush head is predominantly or exclusively formed by the bristle carrier, whereas only the brush body is formed by injecting the hard component into the second mold cavity, and by the respective method for precisely forming the mold cavity geometry as a high-precision component.
The bristle carrier formed in the first mold cavity is, according to the invention, connected to a hard component by means of over-molding, to precisely fill certain parts or almost the entire surface of the brush by the hard component. Further plastic components, in particular soft-elastic components can be formed between the bristle carrier and the hard component by interconnected injection molding steps. After filling the further mold cavity by the hard component, further injection molding steps for filling in particular soft elastic functional elements or surfaces can follow. The further preferred embodiments of the method are left to the expert""s discretion and it is essential for the method according to the invention that the hard component in the further mold cavity can be filled in without restricting the method parameters, and for instance the formation of a precise component directly or indirectly connected with the bristle carrier is possible.
In case of a conceivable procedure, a soft-elastic component, in particular a thermoplastic elastomer is first of all injected to the bristle carrier. Hereby soft-elastic clearing elements, extending as elongated naps parallel to the bristle bundles, may be provided at the bristle carrier The component manufactured in this manner is thereupon rearranged to a further mold cavity and finally over-molded by the hard component. In this procedure, the bristle carrier can be inserted into the further mold cavity in particular in a manner that the solidified bristle carrier fully covers at its end the further mold cavity.
With this embodimnet a component is obtained which does not have surfaces formed by the hard component at the surface penetrated by the bristles. On the other hand, such surfaces are preferably to be provided on the side of the bristle carrier opposite the bristle side that serve as functional surfaces for a connection of the bristle carrier at a handle. The functional surfaces may be formed as catch surfaces to lock the bristle carrier to the handle. If the handle contains the motor of an electric tooth brush, functional surfaces may moreover be provided by the hard component through which the bristle carrier is hingeable, pivotal or rotatably supported. Moreover, the functional surfaces may form connection elements through which the bristle carrier can be connected to and released from the motor. Finally, such functional surfaces may be provided that effect a sealing of the bristle carrier with respect to the handle.
A brush head comprising a plurality of brush head bodies may be manufactured by the method according to the invention, which are for instance coupled via a web encompassed by a soft-elastic material. In such a case, the brush head body bodies is inserted after manufacture of the brush head body into a following mold cavity by means of two-component or injection molding, said mold cavity being larger than the further mold cavity and which is filled by a soft-elastic component. In this manner, one or a plurality of elastic zones can be formed in the brush head and/or at the transition between the brush head and the handle, in which said zones the hard component is at most provided as a thin web and which comprise almost exclusively a soft-elastic component, in particular a thermoplastic elastomer which covers the free spaces between opposing brush head segments and which prevents penetration of dust and/or bacteria.
The above-mentioned over-moldings of a brush head body by soft-elastic mass are for instance known from DE 39 23 495 as an example for a brush head, which is elastically held at the handle, or they are known from WO 97/24048 as an example for elastic head segments. Contrary to this known prior art, the brush head body holding the bristle filaments is manufactured by the method according to the invention by means of two-component injection molding. The brush head body manufactured by means of a two-component injection molding process may of course comprise one or a plurality of elastic zones in which thermoplastic elastomer introduced by means of over-molding a third component is contained, or which is attached at the handle by interposition of an elastic zone containing a thermoplastic elastomer or the like.
In the method according to the invention, a hard component is preferably also used as a first plastic component. This hard component may be for instance polypropylene. The advantages of the method according to the invention can be realized especially favorably when the first mold cavity is filled by a plastic mass which has a relatively high melting index (MFI) whereas the further mold cavity is filled by a hard component that has a relatively low melting index.
In the same manner it is preferred to first of all inject a plastic component having a low plastification temperature into the first mold cavity and to fill the further mold cavity by a hard component having a higher plastification temperature.
Regarding the brush head of the above-mentioned kind, the object underlying the invention is solved in that the brush head body comprises a bristle body encompassing the bristle filaments at the attachment side, said bristle carrier being connected to a hard component Through the hard component, any component, in particular a high-precision component can be formed at the bristle carrier possibly by interposition of a soft-elastic layer or directly, or a segment of the brush body may be formed as a precision component.
If the bristle carrier forms at least a part of the surface of the brush head body penetrated by the bristle filaments, a penetration of dirt, bacteria etc. between the bristle carriers and the hard components embedding the bristle carrier preferably formed as a shell can be prevented in that the bristle carrier is positively connected to the hard component. It is especially preferred to encompass peripherally the bristle carrier by the hard component. Peripheral means that the hard component is provided at the side faces of the brush head extending substantially parallel to the bristle filaments. Additionally, the hard component is preferably also provided at the lower side of the brush head, formed opposite the bristle surface penetrated by the bristle filaments. Since the hard component can be injected at an increased pressure into the second mold cavity, details at the outer surface of the brush head body can be formed at high precision by means of injection molding by the hard component peripherally encompassing the bristle carrier.
Functional surfaces of that type are in particular locking noses etc. by means of which the brush head body is held in a recess formed in the brush head. A respective tooth brush is form instance known from DE-C 196 00 767. The functional surfaces can also be formed at the brush head to connect same to the handle (cf. DE-U-94 20 405).

Method of manufacturing a brush head by way of an injection molding process