White, dyed, dipped, unscented and/or scented candle wax is effectively stabilized against discoloration and fading by the incorporation therein of an s-triazine UV absorber plus a classic hindered amine and/or an antioxidant.

The instant invention pertains to white, dyed, dipped, unscented and/or scented candle wax which is effectively stabilized against discoloration and fading by the incorporation therein of an s-triazine UV absorber plus a classic hindered amine and/or an antioxidant.
Candles have been known for many centuries going back to the eighth century B.C. The nature of candles is described in Ullmann""s Encyclopedia of Industrial Chemistry, Volume A5 at pages 29-30 where it is seen that candles are made from paraffin, beeswax and stearin as basic materials, and where a host of additives may also be present.
It is not surprising that with candles and wax becoming increasingly more important attention was paid as to how to stabilize the said materials. At the National Candle Association Meeting in Houston, 1994, R. van der Vennet presented a paper on xe2x80x9cAntioxidants in Waxxe2x80x94Replacement of BHTxe2x80x9d touting the use of Vitamin E (tocopherol) as an antioxidant to prevent the yellowing of wax when oxidized. WO 94/13736 describes the same invention.
EP 359,488 A3 and EP 133,964 B1 describe stabilized waxes used in cosmetics where the waxes are the same or similar to those used in candles.
EP 5,922 A1 describes lip cosmetics where the waxes are useful in lipsticks and are related to those useful in candles.
U.S. Pat. No. 5,879,694 describes in detail transparent gel candles both in composition and structure. The use of BHT as an antioxidant is mentioned.
At the National Candle Association Technical Meeting on Apr. 16, 1998, F. A. Ballentine et al., presented a paper entitled xe2x80x9cInhibiting Color Fading of Dyed Candles with CYASORB(copyright) Light Absorbersxe2x80x9d in which the general theories of thermal oxidation and photodegradation are discussed along with data on the effect of light absorbers on color stability of dyed candle waxes. The light absorbers compared are 4-octyloxy-2-hydroxybenzophenone UV-531; 4-methoxy-2-hydroxybenzophenone UV-9; 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole UV-5365; 2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole UV-5411 and 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole UV-2337).
U.S. Pat. No. 5,964,905 teaches dyed and scented candle gels containing triblock copolymers and a hydrocarbon oil of high flash point. This reference teaches that a light (UV) absorber may be used to improve the shelf stability of the candle color when exposed to visible or ultraviolet light. Two preferred absorbers are ethylhexyl p-methoxycinnamate (PARSOL(copyright) MCX, Roche) and 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (CYASORB(copyright) 5411, Cytec).
WO 00/22037 teaches the stabilization of solid, shaped and colored wax articles, including candles, using a malonate UV absorber which may optionally contain a hindered amine moiety as part of the malonate compound structure. The wax articles are dyed with a variety of oil soluble dyes and pigments. The samples protected by dimethyl p-methoxybenzylidinemalonate exhibited better resistance to discoloration that did samples stabilized with selected benzotriazole or benzophenone UV absorbers.
Japanese Hei 3-278554 teaches that wax crayons (drawing materials) colored by organic pigments can be stabilized by a hindered amine and/or benzotriazole.
In respect to wax stabilization, the use of selected hindered amines and/or benzotriazole UV absorbers is also known in the prior art as seen in U.S. Pat. Nos. 3,530,084; 4,379,721; 4,616,051 and 5,964,905 and copending applications Ser. Nos. 09/495,495, 09/495,496 and 09/741,583.
None of these references teach the superior performance provided when the s-triazine UV absorbers are used in conjunction with a classic piperidine-based hindered amine and/or an antioxidant to stabilize candle wax.
The object of the invention is to provide for a white and unscented; white and scented; dyed and unscented; dyed and scented; dipped and unscented; or dipped and scented candle wax stabilized by a combination of a s-triazine UV absorber and a classic piperidine-based hindered amine and/or an antioxidant.
The instant invention pertains to a composition which comprises
(a) candle wax which is white and unscented; white and scented; dyed and unscented; dyed and scented; dipped and unscented; or dipped and scented, and
(b) an effective stabilizing amount of a combination of
(i) an s-triazine UV absorber of formula I, II, III, IV, V or VI
xe2x80x83wherein
X and Y are independently phenyl, naphthyl, or said phenyl or said naphthyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof; or X and Y are independently Z1 or Z2;
R1 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, halogen, xe2x80x94SR3, xe2x80x94SOR3 or xe2x80x94SO2R3; or said alkyl, said cycloalkyl or said phenylalkyl substituted by one to three halogen, xe2x80x94R4, xe2x80x94OR5, xe2x80x94N(R5)2, xe2x80x94COR5, xe2x80x94COOR5, xe2x80x94OCOR5, xe2x80x94CN, xe2x80x94NO2, xe2x80x94SR5, xe2x80x94SOR5, xe2x80x94SO2R5 or xe2x80x94P(O)(OR5)2, morpholinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, piperazinyl or N-methylpiperidinyl groups or combinations thereof; or said alkyl or said cycloalkyl interrupted by one to four phenylene, xe2x80x94Oxe2x80x94, xe2x80x94NR5xe2x80x94, xe2x80x94CONR5xe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94OCOxe2x80x94 or xe2x80x94CO groups or combinations thereof; or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above;
R3 is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms;
R4 is aryl of 6 to 10 carbon atoms or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; or straight or branched chain alkenyl of 2 to 18 carbon atoms;
R5 is defined as is R4; or R5 is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms; or R5 is a group for formula
T is hydrogen, oxyl, hydroxyl, xe2x80x94OT1, alkyl of 1 to 24 carbon atoms, said alkyl substituted by one to three hydroxy; benzyl or alkanoyl of 2 to 18 carbon atoms;
T1 is alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkenyl of 2 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated or unsaturated bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms or aryl of 6 to 10 carbon atoms or said aryl substituted by one to three alkyl of 1 to 4 carbon atoms;
R2 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl or said cycloalkyl substitute by one to four halogen, epoxy, glycidyloxy, furyloxy, xe2x80x94R4, xe2x80x94OR5, xe2x80x94N(R5)2, xe2x80x94CON(R5)2, xe2x80x94COR5, xe2x80x94COOR5, xe2x80x94OCOR5, xe2x80x94OCOC(R5)xe2x95x90C(R5)2, xe2x80x94C(R5)xe2x95x90CCOOR5, xe2x80x94CN, xe2x80x94NCO, or
xe2x80x83or combinations thereof; or said alkyl or said cycloalkyl interrupted by one to four epoxy, xe2x80x94Oxe2x80x94, xe2x80x94NR5xe2x80x94, xe2x80x94CONR5xe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94OCOxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94C(R5)xe2x95x90C(R5)COOxe2x80x94, xe2x80x94OCOC(R5)xe2x95x90C(R5)xe2x80x94, xe2x80x94C(R5)xe2x95x90C(R5)xe2x80x94, phenylene or phenylene-G-phenylene in which G is xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94CH2xe2x80x94 or xe2x80x94C(CH3)2xe2x80x94 or combinations thereof, or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above; or R2 is xe2x80x94SO2R3 or xe2x80x94COR6;
R6 is straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 12 carbon atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms, xe2x80x94R7COOH or xe2x80x94NHxe2x80x94R8xe2x80x94NCO;
R7 is alkylene of 2 to 14 carbon atoms or phenylene;
R8 is alkylene of 2 to 24 carbon atoms, phenylene, tolylene, diphenylmethane or a group
R1, R1xe2x80x2 and R1xe2x80x3 are the same or different and are as defined for R1;
R2, R2xe2x80x2 and R2xe2x80x3 are the same or different and are as defined for R2;
X, Xxe2x80x2, Y and Yxe2x80x2 are the same or different and are as defined for X and Y;
t is 0 to 9;
L is straight or branched alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene substituted or interrupted by cyclohexylene or phenylene; or L is benzylidene; or L is xe2x80x94Sxe2x80x94, xe2x80x94Sxe2x80x94Sxe2x80x94, xe2x80x94Sxe2x80x94Exe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94SOxe2x80x94Exe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94Exe2x80x94SO2xe2x80x94, xe2x80x94CH2xe2x80x94NHxe2x80x94Exe2x80x94NHxe2x80x94CH2xe2x80x94 or
E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene interrupted or terminated by cycloalkylene of 5 to 12 carbon atoms;
n is 2, 3 or 4;
when n is 2; Q is straight or branched alkylene of 2 to 16 carbon atoms; or said alkylene substituted by one to three hydroxy groups; or said alkylene interrupted by one to three xe2x80x94CHxe2x95x90CHxe2x80x94 or xe2x80x94Oxe2x80x94; or said alkylene both substituted and interrupted by combinations of the groups mentioned above; or Q is xylylene or a group xe2x80x94CONHxe2x80x94R8xe2x80x94NHCOxe2x80x94, xe2x80x94CH2CH(OH)CH2Oxe2x80x94R9xe2x80x94OCH2CH(OH)CH2xe2x80x94, xe2x80x94COxe2x80x94R10xe2x80x94COxe2x80x94, or xe2x80x94(CH2)mxe2x80x94COOxe2x80x94R11xe2x80x94OOCxe2x80x94(CH2)mxe2x80x94, where m is 1 to 3; or Q is
R9 is alkylene of 2 to 50 carbon atoms; or said alkylene interrupted by one to ten xe2x80x94Oxe2x80x94, phenylene or a group -phenylene-G-phenylene in which G is xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94CH2xe2x80x94 or xe2x80x94C(CH3)2xe2x80x94;
R10 is alkylene of 2 to 10 carbon atoms, or said alkylene interrupted by one to four xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94; or R10 is arylene of 6 to 12 carbon atoms;
R11 is alkylene of 2 to 20 carbon atoms or said alkylene interrupted by one to eight xe2x80x94Oxe2x80x94;
when n is 3, Q is a group xe2x80x94[(CH2)mCOO]3xe2x80x94R12 where m is 1 to 3, and R12 is an alkanetriyl of 3 to 12 carbon atoms;
when n is 4, Q is a group xe2x80x94[(CH2)mCOO]4xe2x80x94R13 where m is 1 to 3, and R14 is an alkanetetrayl of 4 to 12 carbon atoms;
Z1 is a group of formula
Z2 is a group of formula
xe2x80x83where
r1 and r2 are independently of each other 0 or 1;
R14, R15, R16, R17, R18, R19, R20, R21, R22 and R23 are independently of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl; or R17 and R18 or R22 and R23 together with the phenyl radical to which they are attached are a cyclic radical interrupted by one to three xe2x80x94Oxe2x80x94 or xe2x80x94NR5xe2x80x94; and
(ii) a classic piperidine-based hindered amine,
wherein the ratio by weight of (i) to (ii) is from 10:1 to 1:10.
In another embodiment of the instant invention, the s-triazine UV absorbers are those of formula I where
X and Y are the same or different and are phenyl or said phenyl substituted by one to three alkyl of 1 to 6 carbon atoms, halogen, hydroxy or alkoxy of 1 to 12 carbon atoms; or Z1 or Z2;
R1 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or halogen;
R2 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl or said cycloalkyl substituted by one to three xe2x80x94R4, xe2x80x94OR5, xe2x80x94COOR5, xe2x80x94OCOR5 or combinations thereof; or said alkyl or cycloalkyl interrupted by one to three epoxy, xe2x80x94Oxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94OCOxe2x80x94 or xe2x80x94COxe2x80x94;
R4 is aryl of 6 to 10 carbon atoms or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof;
R5 is defined as is R4; or R5 is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms;
Z1 is a group of formula
Z2 is a group of formula
xe2x80x83where r1 and r2 are each 1; and
R14, R15, R16, R17, R18, R19, R20, R21, R22 and R23 are independently hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, or alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl.
In still another embodiment of the instant invention, the s-triazine UV absorbers are those of formula II where
X is phenyl, naphthyl or said phenyl or said naphthyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof; or X is Z1;
R1 and R1xe2x80x2 are independently as defined for R1; and
R2 and R2xe2x80x2 are independently as defined for R2.
Another embodiment of the instant invention involves the s-triazine UV absorbers of formula III where
R1, R1xe2x80x2 and R1xe2x80x3 are independently as defined for R1; and
R2, R2xe2x80x2 and R2xe2x80x3 are independently as defined for R2.
In still another embodiment of the instant invention, the s-triazine UV absorbers are those of formula VI
X and Y are independently phenyl or said phenyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof; or X and Y are independently Z1 or Z2; and
L is straight or branched alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene substituted or interrupted by cyclohexylene or phenylene.
Another embodiment of the instant invention involves the s-triazine UV absorbers of formula I where
X and Y are the same or different and are phenyl or said phenyl substituted by one to three alkyl of 1 to 6 carbon atoms; Z1 or Z2;
R1 is hydrogen or phenylalkyl of 7 to 15 carbon atoms;
R2 is hydrogen, straight or branched chain alkyl of 1 to 18 carbon atoms; or said alkyl substituted by one to three xe2x80x94R4, xe2x80x94OR5 or mixtures thereof; or said alkyl interrupted by one to eight xe2x80x94Oxe2x80x94 or xe2x80x94COOxe2x80x94;
R4 is aryl of 6 to 10 carbon atoms;
R5 is hydrogen;
Z1 is a group of formula
Z2 is a group of formula
xe2x80x83where
r1 and r2 are each 1; and
R14, R15, R16, R17, R18, R19, R20, R21, R22 and R23 are each hydrogen
Specific s-triazine UV absorbers which are useful in the instant invention include
(a) 2,4-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-6-mesityl-s-triazine;
(b) 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine, CYASORB(copyright) 1164, Cytec;
(c) 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;
(d) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s-triazine;
(e) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-5-xcex1-cumylphenyl]-s-triazine;
(f) reaction product of 2,4,6-tris(2,4-dihydroxyphenyl)-s-triazine with isooctyl xcex1-halopropionate;
(g) 2-(2,4-dibutyloxyphenyl)-4,6-bis(2-hydroxy-4-butyloxyphenyl)-s-triazine;
(h) 2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine;
(i) 2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;
(j) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;
(k) 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-di-butyloxyphenyl)-s-triazine;
(l) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-xcex1-cumylphenyl]-s-triazine; (* denotes a mixture of octyloxy, nonyloxy and decyloxy groups)
(m) methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine}, methylene bridged dimer mixture bridged in the 3:5xe2x80x2, 5:5xe2x80x2 and 3:3xe2x80x2 positions in a 5:4:1 ratio;
(n) 2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine;
(o) 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-xcex1-cumylphenyl)-s-triazine; or
(p) 2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine.
In another embodiment of the instant invention, the s-triazine UV absorber of component (b)(i) is
(a) 2,4-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-6-mesityl-s-triazine;
(f) reaction product of 2,4,6-tris(2,4-dihydroxyphenyl)-s-triazine with isooctyl xcex1-halopropionate;
(h) 2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine;
(l) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-xcex1-cumylphenyl]-s-triazine; (* denotes a mixture of octyloxy, nonyloxy and decyloxy groups) or
(n) 2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine.
In another embodiment of the invention, the ratio by weight of (i) to (ii) is from 4:1 to 1:4.
In still another embodiment of the invention, the ratio by weight of (i) to (ii) is from 2:1 to 1:2.
In still another embodiment of the invention, the effective amount of the s-triazine UV absorber plus the hindered amine in the candle wax is 0.01 to 10% by weight based on the wax.
In another embodiment of the invention, the effective amount of the s-triazine UV absorber plus hindered amine in the candle wax is 0.1 to 2% by weight based on the wax.
In another embodiments of the invention, the effective amount of the s-triazine UV absorber plus hindered amine in the candle wax is 0.1 to 0.5% by weight based on the wax.
The classic piperidine-based hindered amines useful in the instant invention are those compounds having a substituted 2,2,6,6-tetraalkylpiperidine moiety where the nitrogen atom is substituted by hydrogen, alkyl, cycloalkyl, acyl or acyloxy.
Typical examples of such classic piperidine-based hindered amines are selected from the group consisting of
(a) bis(2,2,6,-tetramethylpiperidin-4-yl)sebacate,
(b) bis(1,2,2,6,-pentamethylpiperidin-4-yl)sebacate,
(c) di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,
(d) 4-benzoyloxy-2,2,6,6-teramethylpiperdine,
(e) 4-stearyloxy-2,2,6,6-tetramethylpiperidine,
(f) tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,
(g) polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4xe2x80x2-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),
(h) polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid,
(i) polycondensation product of 4,4xe2x80x2-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromoethane,
(j) tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate,
(k) tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate,
(l) polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4xe2x80x2-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),
(m) N,Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,
(n) octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate),
(o) N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,
(p) N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,
(q) N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,
(r) 4-C15-C17alkanoyloxy-2,2,6,6-tetramethylpiperidine,
(s) polycondensation product of 2,4-dichloro-6-cyclohexylamino-s-triazine and 4,4xe2x80x2-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),
(t) 1,5-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,5-diaza-4-oxopropane,
(u) copolymer of methyl methacrylate, ethyl acrylate and 2,2,6,6-tetramethylpiperidin-4-yl acrylate,
(v) copolymer of N-octadecylmaleimide, styrene and N-(2,2,6,6-tetramethylpiperidin-4yl)maleimide,
(w) 1,3,5-tris[3-(2,2,6,6-piperidin-4-ylamino)-2-hydroxy-propyl) isocyanurate,
(x) olefin copolymer containing units derived from N-[2-(2,2,6,6-tetramethylpiperidin-4-yl)oxalamid-1-yl]maleimide,
(y) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5,1,11,2]heneicosane,
(z) C12-C14alkyl 3-(2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5,1,11,2]heneicosane-20-yl)propionate,
(aa) reaction product of epichlorohydrin and 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5,1,11,2]heneicosane,
(bb) 1,3-di(2,2,6,6-tetramethylpiperidin-4-yl) 2,4-ditridecyl butanetetracarboxylate,
(cc) 1,3-di(1,2,2,6,6-pentamethylpiperidin-4-yl) 2,4-ditridecyl butanetetracarboxylate,
(dd) polycondensation product of 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, tetramethyl 1,2,3,4-butanetetra-carboxylate and 2,2,6,6-tetramethyl-4-hydroxypiperidine.
(ee) polycondensation product of 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, tetramethyl 1,2,3,4-butanetetra-carboxylate and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine,
(ff) 1,4-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2,2-dimethyl-1,4-diaza-4-oxopropane,
(gg) reaction product of 4-amino-2,2,6,6-tetramethylpiperidine and tetramethylolacetylenediurea,
(hh) 1,6-hexamethylenebis[N-formyl-N-(2,2,6,6-tetramethylpiperidin-4-yl)amine],
(ii) copolymer of N-(2,2,6,6-tetramethylpiperdin-4-yl)maleimide and a C20-C24-alpha-olefin,
(jj) poly[3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl-methyl-siloxane],
(kk) polycondensation product of 2,4-dichloro-6-[N-butyl-N-(2,2,6,6-tetramethylpiperidin-4-yl)amino]-s-triazine and 1,10-diamino-4,7-diazadecane, or
(ll) dodecyl 3-(2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5,1,11,2]heneicosane-20-yl)propionate.
In another embodiment of the instant invention, the classic hindered amine is
(a) bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,
(b) bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,
(c) di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,
(g) polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4xe2x80x2-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),
(h) polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, or
(m) N,Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane.
In another embodiment of the invention, a further UV absorber which is benzotriazole, a benzophenone, an xcex1-cyanoacrylate, an oxanilide, a cinnamate, a malonate, a benzoate or a salicylate, or a mixture thereof is also present.
In another embodiment of the invention, the UV absorber is a benzotriazole or a benzophenone.
Examples of such additional UV absorbers useful in the instant invention are
(a) 4-octyloxy-2-hydroxybenzophenone;
(b) 4-methoxy-2-hydroxybenzophenone;
(c) 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole;
(d) 2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole;
(e) 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;
(f) octyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;
(g) 2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;
(h) 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole;
(i) 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;
(j) 5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;
(k) 2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)-2H-benzotriazole;
(l) 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole;
(m) 2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;
(n) 2-[2-hydroxy-3,5-di(xcex1,xcex1-dimethylbenzyl)phenyl]-2H-benzotriazole;
(o) 2-[2-hydroxy-3-(xcex1,xcex1-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;
(p) 2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole;
(q) 2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.
(r) 2-ethylhexyl p-methoxycinnamate;
(s) 4-methoxy-2,2xe2x80x2-dihydroxybenzophenone; or
(t) 4,4xe2x80x2dimethoxy-2,2xe2x80x2-dihydroxybenzophenone.
Still other examples of UV absorbers useful in the instant invention are
(a) 4-octyloxy-2-hydroxybenzophenone;
(b) 4-methoxy-2-hydroxybenzophenone;
(d) 2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole;
(o) 2-[2-hydroxy-3-(xcex1,xcex1-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;
(p) 2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole; or
(q) 2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.
Another embodiment of the instant invention involves a composition wherein an antioxidant which is a phenolic antioxidant, phosphite, nitrone, amine oxide or hydroxylamine, or mixture thereof is also present.
Examples of the above-embodiment are wherein the effective amount of s-triazine UV absorber in combination with the hindered amine compound and an antioxidant is 0.01 to 10% by weight based on the wax.
Another embodiment is where the effective amount of s-triazine UV absorber in combination with the hindered amine compound and an antioxidant is 0.1 to 2% by weight based on the wax.
Still another embodiment is where the effective amount of s-triazine UV absorber in combination with the hindered amine compound and an antioxidant is 0.1 to 0.5% by weight based on the wax.
Examples of the antioxidants useful in this invention are
n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,
neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate),
di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),
2,6-di-tert-butyl-p-cresol,
2,2xe2x80x2-ethylidene-bis(4,6-di-tert-butylphenol),
1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate,
1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,
1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,
3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol,
hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),
1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,
N,Nxe2x80x2-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),
calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),
ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate],
octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,
bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide,
N,N-di-(C12-C24alkyl)-N-methyl-amine oxide, or
N,N-dialkylhydroxylamine prepared from di(hydrogenated tallow)amine by direct oxidation.
Still other embodiments of antioxidants useful in the instant invention are
neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),
n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
2,6-di-tert-butyl-p-cresol, or
2,2xe2x80x2-ethylidene-bis(4,6-di-tert-butylphenol).
It should be noted that candles contain a host of various components. The base materials may be made up of the following:
paraffin wax,
natural oils,
polyamide plus fatty acid/ester,
fatty acids such as stearin,
opacifiers,
beeswax,
glycerides plus oxidized wax,
alcohols, and
ethylene oligomers.
Candles also contain a number of additives such as the following:
mold release agents,
fragrances,
insect repellents or insecticides,
hardeners,
crystal modifiers,
clarifiers,
guttering reducers,
colorants,
f.p. control agents,
stretchability improvers,
gelling agents,
extrusion aids, and
vortex reducers.
Each of the various components are meant to control or modify the properties of the candle to insure proper burning, reduce channelling, aid in uniform melting, and the like. The colorants and fragrances obviously are there to provide the proper color, scent or other aesthetic appeal.
Of increasing importance are the transparent gel candles which look like clear glass, but which burn like a classical candle. As is discussed in detail in U.S. Pat. No. 5,879,694, the relevant parts of which are incorporated herein by reference, these gel candles usually contain a copolymer selected from the group consisting of a triblock, radial block, diblock or multiblock copolymer classically made up of at least two thermodynamically incompatible segments containing both hard and soft segments. Typical of such block copolymers is KRATON(copyright) (Shell Chemical Co.) which consists of block segments of styrene monomer units and rubber monomer or comonomer units. The most common structure found in KRATON(copyright) D series is a linear ABA block with styrene-butadiene-styrene (SBS) or styrene-isoprene-styrene (SIS).
The following examples are meant for illustrative purposes only and are not to be construed to limit the instant invention in any manner whatsoever.
Raw Materials
Wax samples are supplied by the Candle-Lite Corporation. These samples contain dyes and fragrances.
The UV absorbers and hindered amine stabilizers are obtained from the Ciba Speciality Chemicals Corporation.
Sample Preparation
The wax samples obtained from the Candle-Lite Corporation already contain a dye and a fragrance (scent). In these cases, the wax is melted and the appropriate stabilizer(s) is (are) added and dissolved in the molten wax. The stabilized wax is then poured into five (5) 44 mm diameter aluminum pans giving five (5) wax disks.
Sample Exposure
Triplicate samples of each disk are exposed under a bank of six (6) cool-white fluorescent lamps (40 watts) or under a bank of six (6) UV lamps having a wavelength of 368 nm with the test samples being twelve (12) inches (30.48 cm) below the lamps.
Dye color fade (or color change) is measured by a Macbeth ColorEye Spectrophotometer with a 6 inch integrating sphere. The conditions are: 10 degree observer; D65 illuminant and 8 degree viewing angle.
Initial color measurements are taken using the above parameters. The L, a and b values are calculated using the CIE system from the reflectance values. YI is calculated from the L, a and b values. Subsequent measurements are taken at specified intervals. Delta L, a, b and YI values are simply the difference between the initial values and the values at each interval. Delta(xcex94) E is calculated as follows:
[(Delta L)2+(Delta a)2+(Delta b)2]xc2xd=Delta E.

Candle wax stabilized with s-triazines/hals


The invention provides a massage machine of the chair type having contact portions for applying a pressing force concentrically or dividedly so as to massage the user with the desired intensity. The machine comprises a massage unit having a first therapeutic finger for giving tapping massage to the upper part or the upper to frontal part of the shoulder of the user, and a second therapeutic finger for giving tapping massage to the back or the back to the posterior part of the shoulder. The fingers each have a portion to be brought into contact with the user at the forward end of an arm. The arms are pivotally movable independently of each other by respective finger drive means.

Various massage machines or devices are known for pressing or stimulating the shoulders, waist or other parts of the human body to remove stiffness. According to the type, such devices can be divided into the chair type, bed type and handy type. With respect to the mode of action on the affected part, these devices resort to finger pressure, vibrations or electrical stimulation.
FIG. 13 shows a massage machine 90 of the chair type which is especially in wide use among other massage devices. The machine 90 comprises a chair 91 for the person to be massaged (hereinafter referred to as the "user"), and a pair of therapeutic fingers 95, 95 projecting forward from the backrest 92 of the chair. Each of the finger 95 comprises an arm 93 coupled to a motor (not shown) for driving the finger, and a contact portion 94 provided at the forward end of the arm 93 and adapted to be brought into contact with the affected part of the user. When the motor is driven, the therapeutic fingers 95, 95 perform a tapping operation vertically of the machine or a lateral kneading operation to massage the user.
Although adapted to massage the posterior part of the user's shoulder and the back, the massage machine thus constructed is unable to massage the upper part or the upper to frontal part of the shoulder.
Furthermore, the massage machine continually massages a particular portion of the affected part, so that if the machine is used for a prolonged period of time, the affected part will feel painful or becomes insensitive, or the user is likely to become tired of massage.
The massage machine acts on the user by pressing the affected part from behind, so that if used continuously, the upper part of the user's body is gradually pushed forward, failing to remain in position stably. Thus, the machine is unable to produce a satisfactory massage effect.
Additionally, when the machine is used for massaging the affected part of the user, especially the back or the waist, it is impossible to alter the area of the pressing contact of the therapeutic finger contact portion 94 with the user's body. In other words, the pressing force to be applied locally by the contact portion can not be increased or decreased to give the desired intensity.
An object of the present invention is to provide a chair-type massage machine and massage unit which are adapted to give a wide variety of massage operations.
Another object of the invention is to provide a massage machine of the chair type for applying a pressing force concentrically or dividedly so as to massage the user with the desired intensity.


A spectrograph with a first concave spectrographic diffraction grating is positioned to receive light from the input light source is configured to provide a diffracted light output dispersing the components of the input light source in a first direction. The dispersion forms the input light into an intermediate spectra. The intermediate spectra is formed in a focal surface by the once diffracted light. A slit is substantially positioned on the focal surface. A second concave diffraction grating is positioned to receive once diffracted light from the slit and configured to provide a twice diffracted light output, the second concave diffraction grating dispersing the components of the input light source in a second direction. The second direction is different from the first direction, the dispersion forming the input light into an output spectra.

It is known in the art to use various optical modules that are assembled into a desired configuration to perform a single specified optical function. Such configuration may take the form of a scientific instrument, or may find employment in a commercial spectroscopy application. It is usually advantageous to make each module as compact as possible.
A spectroscope, an instrument which produces a spectrum from input light, is one particularly useful example of such an optical instrument. The term "spectrum" is meant to encompass less than a complete range of wavelengths, for example, the collection of wavelengths emitted by a sample under excitation or passed by a sample filtering input light energy. Another example is a spectrograph which is a spectroscope provided with a recording device, or other light-capture means, or the like to receive and record or otherwise process the spectrum generated. The present invention relates to an optical arrangement particularly useful in spectrographs, and that term will be used hereinafter. However it will be understood that the novel optics described herein can be employed in spectroscopes or spectrometers and generally all applications where recording, quantification or similar capabilities are required and the invention extends to such novel spectroscopic and spectrometric applications employing the inventive optics. To the extent that the invention may be applied to output a single spectral band or to provide a scanned output comprising a series of individual spectral bands, the term "spectrometer" should also be understood to include monochromators.
Diffraction grating spectrographs use one or more diffraction gratings to diffract input light into a spectrum of specific wavelengths or spectral bands.
In a typical configuration, spectrographs are designed to select a single wavelength, or a narrow spectral band from the input light, for examination or recordal.
In one known embodiment of spectrometer employing a planar diffraction grating, a concave mirror is illuminated by a point source whose spectrographic composition is to be analyzed. The light from the point source is collimated by the concave mirror to form a parallel bundle of rays, which are caused to fall upon the surface of a planar diffraction grating. This concave mirror is known as a collimator in a typical spectrometer instrument. Because the planar diffraction grating has a number of grooves etched in its surface, light falling on the surface of the diffraction grating is diffracted, that is, reflected at an angle which is a function of the wavelength of the light. If the input light source comprises a number of wavelengths, the result is that light of different wavelengths will be diffracted, or reflected, at an angle which is a function of wavelength.
The diffracted light may then be received by a second concave mirror which focuses the diffracted light to form an image of the point source under analysis. However, because light of different wavelengths has been diffracted at different angles, the point source is imaged by the second concave mirror, also known as a focusing mirror, at different points for different wavelengths. Accordingly, it is possible to select out individual wavelengths, or more precisely a narrow region of the spectrum, or spectral band, consisting essentially of a single wavelength, to measure the intensity of the same and to utilize this information, for example for elemental analysis of an emissive source material.
Spectrometric elemental analysis of samples has many industrial uses. For example, in the case of the analysis of industrial slag, such as might be obtained from a crucible filled with molten metal in a steel furnace, the slag may be exited into a plasma, and the emission spectrum analyzed and measured with a spectrometer. The wavelengths appearing in the plasma emission spectra indicate the nature and quantity of the impurities in the slag, enabling plant operators to adjust production parameters to achieve a desired product.
While the above discussion has centered on spectrometer devices using mirrors, and such devices are usually preferred because of the quality of imaging using mirrors, it is possible to construct devices using focusing lenses, such as convex lenses or compound multielement lenses having an overall convex optical characteristic. In principle, it is also possible to combine lenses and mirrors in an instrument.
It is also noted that diffraction gratings in spectrometers may be either classical mechanically ruled diffraction gratings of the type invented and made by applicant's assignee at the beginning of the 1800's, or holographic diffraction gratings of the type manufactured by applicant's assignee since the 1960's.
It is also known that spectrometers may be constructed using concave diffraction gratings, such as concave holographic diffraction gratings of the type invented by Flamand in the late 1960's working at the applicant company as illustrated by his U.S. Pat. No. 3,628,849.
A Littrow-mounted system is a relatively common method of utilizing large plane reflection gratings, providing simplicity and good optical quality arising from the use of a single mirror to perform both collimating and focusing functions. Moreover, in this configuration, the collimating and focusing functions are both performed in the same geometric space, resulting in efficient use of that space. In a typical Littrow setup, a mirror delivers parallel incident light from an input point source to the grating, and focuses diffracted light received from the grating to an output point often proximate the input point source. In such devices, a single mirror acts as both collimator and focusing element at once, minimizing the number of optical elements required.
In addition to its simplicity, employing the Littrow configuration is particularly desirable for its high quality output. Because the input and output light beams traverse the same optical path, in opposite directions, optical aberrations in the collimating and focusing components are auto-corrected, or self compensating, so that image quality is diffraction limited, i.e. limited by the physical properties of the optical system not by the deficiencies of the optics.
A particular drawback of such conventional Littrow-mounted grating configurations is the difficulty and expense of providing a grating with a central optical opening. Another drawback is that undue stray light may be returned to the aperture by the mirror. It would be desirable to provide a spectrometer or comparable optical system, which did not suffer from these drawbacks.

Double grating three dimensional spectrograph


Systems and methods that facilitate performing multiple transactions at once using a vehicle based wallet are disclosed herein. The vehicle based wallet can link to a plurality of mobile wallets and perform singular transactions with ATMs and POS machines, the singular transactions being a group transaction associated with one or more of the mobile wallets. The vehicle based wallet can collect intended transactions between the ATMs and the POS machines and the mobile wallets, and then gather them together and perform a single group transaction made up of the individual transactions for multiple people that are within the vehicle.

Automated teller machines ("ATMs") and point of sale ("POS") machines perform transactions one at a time. If there are multiple people who would like to perform a transaction, each person has to be verified, request a transaction and then complete the transaction. If a vehicle drives up to an ATM and more than one person wishes to perform a transaction then multiple transactions are required. Likewise, if there are multiple people in a vehicle and they are splitting a transaction (such as a gas purchase or paying for tolls) there is no easy way for the group to divide the payment besides exchanging cash with one another. This can lead to people tracking debts or can lead to longer wait times at the pumps or tolls while individuals in a single vehicle divide the cost amongst each other.

Device enabled identification and authentication


A media file processing method, comprising: receiving a request for downloading a target streaming media file; obtaining, in response to the request, a uniform resource locator (URL) of the target streaming media file; determining, according to first pattern information of a header of the URL, whether the target streaming media file is a streaming media file of a Microsoft Media Server (MMS) Protocol; in accordance with a determination that the target streaming media file is a streaming media file of the MMS Protocol, determining, according to a preset correspondence between URL pattern information and a plurality of network communication protocols, a first network communication protocol of the plurality of network communication protocols, that corresponds to the first pattern information of the header of the URL as a target network communication protocol; and obtaining the target streaming media file from a target server by using the target network communication protocol.

With the popularity of mobile terminals such as smartphones, more users become accustomed to viewing multimedia files on the Internet by using mobile terminals, for example, watching videos provided by video websites on smartphones. Viewing multimedia files by using mobile terminals by a user is often implemented based on a streaming media protocol. The streaming media refers to a media format of implementing online playing by means of streaming transmission. A playback-while-download service function can be implemented by using the streaming media protocol.
Currently, common streaming media protocols mainly include the HLS Protocol (HTTP Live Streaming Protocol), the RTSP Protocol (Real Time Streaming Protocol), the RTP Protocol (Real-time Transport Protocol), the MMS Protocol (Microsoft Media Server Protocol), and the like. The existing multimedia players in the mobile terminal usually support the HLS Protocol and the RTSP/RTP Protocol, but do not support the MMS Protocol. Therefore, a user cannot download or view multimedia files of the MMS Protocol on a mobile terminal.

Streaming media file processing method and apparatus

TENCENT TECHNOLOGY (SHENZHEN) COMPANY LIMITED


A sensor (SEN6a) is provided for detecting a presence of a document sheet at a specified position during a transit path of document sheets supplied. According to detection output from this sensor (SEN6a), a continuous presence time of a document sheet is obtained, and if the continuous presence time obtained is longer than the continuous document presence time obtained last time, this is regarded as an indication of a multiple feed of document sheets, and the feeding of document sheets is stopped.

1. Field of the Invention
The present invention relates to an automatic document feeder for automatically feeding a plurality of documents, such as document sheets, to be copied.
2. Description of the Related Art
In an automatic document feeder, particularly in a recycle document handler, a mechanism is provided which prevents simultaneous feeding of a plurality of document sheets lying one upon another (hereafter referred to as a multiple feed). Nevertheless, a multiple feed of document sheets (originals) sometimes occurs.
There is a prior art for preventing a multiple feed when copies are made by using a recycle document handler (Japanese Patent Application Laying Open (KOKAI) No. 52-119940). In this prior art, when a set of original sheets has been copied, the number of document sheets presented for copying is stored in memory. This number is compared with the number of document sheets circulated for copying after the next set of document sheets has been copied. When these numbers differ, a multiple feed is indicated, and the document handler is shut down.
According to the prior art mentioned above, it is after a set of document sheets has been circulated that a decision can be made whether a multiple feed has occurred. Until then, copying of the document sheets is continued. A resulting problem is that many document sheets which are involved in a multiple feed are not copied. Above all, when duplex copying is performed, there is another problem that ineffective copying occurs in which front and back combinations of the contents of the document sheets are displaced with respect to each other by a multiple feed.
When the number of document sheets is counted and the sheets are copied according to the counted number, if a multiple feed occurs, this results in a wrong counting of the number of document sheets and the copying operation is controlled according to a wrong number of document sheets. If in this case duplex copying is performed on a number of copying paper from simplex document sheets, many copies are made by ineffective copying in which the front and back combinations of the contents of document sheets are displaced with respect to each other.


A method determines a license plate layout configuration. The method includes generating at least one model representing a license plate layout configuration. The generating includes segmenting training images each defining a license plate to extract characters and logos from the training images. The segmenting includes calculating values corresponding to parameters of the license plate and features of the characters and logos. The segmenting includes estimating a likelihood function specified by the features using the values. The likelihood function measures deviations between an observed plate and the model. The method includes storing a layout structure and the distributions for each of the at least one model. The method includes receiving as input an observed image including a plate region. The method includes segmenting the plate region and determining a license plate layout configuration of the observed plate by comparing the segmented plate region to the at least one model.

The present disclosure relates to a method and apparatus for determining a license plate layout configuration. It is appreciated that the present exemplary embodiments are also amendable to other like applications.
An automatic license plate recognition (APLR) system is a vehicular surveillance system that captures images of moving or parked vehicles using a still or video camera. The system locates a license plate in the image, segments the characters in the plate, and uses optical character recognition (OCR) to determine the license plate number. The APLR system often functions as a core module for an intelligent transportation infrastructure system as its many uses can include monitoring traffic flow, enforcing traffic laws, and tracking criminal suspects.
Character segmentation is used to find the individual characters on the plate. Character segmentation presents multiple challenges to conventional APLR systems. One challenge is that jurisdictions may use different layouts, so the system must be able to recognize multiple layouts to be effective. Yet, at the same time, some jurisdictions use similar license plate protocols. For example, a number of states in the U.S. may group equal numbers of characters together between spaces and/or logos. A conventional system relies on a user for confirming that the license plate number correlates to the correct state.
Another challenge associated with character segmentation is the ability to distinguish characters from other objects that form part of the plate or obscure the plate. Screws, dirt, logos, graphics, plate borders, and plate frames can all affect the number of characters that the system detects on the plate. The objects can affect the boundaries drawn between segments and, thus, the ability for the system to distinguish the final output.
The effects of different imaging conditions also present a challenge to character segmentation. Overexposure, reflection, and shadows may result from low contrast, between the image and background, and poor or uneven lighting. There is a need for an ALPR system that is robust enough to handle different conditions.
There is a low tolerance for segmentation error made by an ALPR system because its many applications require high accuracy. Therefore, a need exists for an ALPR system that improves accuracy by reducing a risk of over- and under segmenting, determining erroneous results, and rejecting plate localization errors.

License plate character segmentation using likelihood maximization


A multifunctional broad spectrum antimicrobial composition is described. The composition can be incorporated into a wood preservative, or used as an additive to provide antimicrobial properties to water-based wood coatings. The composition is a concentrated water-miscible emulsion containing 3-iodo-2-propynyl N-butylcarbamate (IPBC), carbendazim (BCM) and propiconazole (PPCZ), and has antimicrobial activity against a wide variety of fungal organisms, including surface molds, blue stain fungi and wood rotting fungi. The composition can act as an in-can preservative and is useful for antimicrobial protection of wood and wood-based substrates.

The present application is directed to an antimicrobial composition for protecting wood. More specifically, the present application is directed to a multifunctional broad spectrum antimicrobial composition which can be incorporated into a wood preservative, or can be used as an antimicrobial additive in water-based wood and wood composite coatings.
Wood surfaces, such as those on buildings and other structures which are exposed to the environment, are susceptible to attack by microbes such as fungi or bacteria and other pests. For example, in areas such as the Lower Mainland of British Columbia, mold growth on attic roof components, especially on wood framing and sheathing, can occur because of roof leaks or water vapor condensation. When air-borne fungal spores and/or tiny air-borne mycelia fragments land on wet or damp wood surfaces, initial mold culture can become established and later proliferate into large colonies. Attempts to prevent the significant condensation problem in such areas by re-designing roofs have not so far successfully addressed the issue.
Fungal attack of wood surfaces can compromise or destroy the structural integrity of the wood, as well as damage its appearance. As well, mold colonies can release high levels of mycotoxins to prevent invasion by competitive organisms. As a result, apart from cosmetic problems, mold growth can cause adverse health effects in humans, and considerably reduce the commercial value of structures.
Coatings and preservatives for such wood surfaces therefore often include antimicrobial compounds to protect the wood from damage caused by such microbes. A wide variety of antimicrobial compounds are known to be used in such wood preservatives and coatings. However, in many cases, such antimicrobial compounds are less effective against some species than others, and may need to be present at relatively high levels to have broad spectrum effectiveness against an adequate range of microbes. Alternatively, combinations of individual antimicrobial products, each of which individually has effectiveness against a specific species or groups of species, may be necessary to achieve broad spectrum effectiveness against the desired range of microbes.
For some applications of wood coatings, it is desirable that such antimicrobial compounds be present at low levels or absent. Many such antimicrobial compounds can be harmful to humans or animals. Thus, if it is likely that humans or animals will come into contact with a coated wood surface, it is desirable to prevent or minimize exposure to potentially harmful levels of antimicrobial compounds caused by such contact. Furthermore, in some cases, wood surfaces may not be exposed to an environment where attack by microbes is a substantial risk, and therefore would not need a high level of antimicrobial protection. In such cases, there would be no need to risk exposing users to high levels of antimicrobial compounds during application of a coating. Thus, manufacturers who wish to provide a choice of coatings to their customers must develop a number of different antimicrobial or non-antimicrobial formulations at additional effort and cost.
Therefore, there is a need for an antimicrobial composition which can be conveniently stored and diluted as needed to provide a wood preservative, or which can be added to wood preservative and wood coating formulations so as to provide the formulations with antimicrobial properties as desired. In this way, coating manufacturers can readily achieve alternative antimicrobial protection for existing coatings without the need for costly or time-intensive research. In some cases, non-antimicrobial coatings, such as interior paints and stains, could be readily adapted for applications requiring antimicrobial properties.
In addition, it is desirable to provide an antimicrobial composition which has antimicrobial activity against a range of wood-attacking microbes, so as to reduce the need for treatment with multiple products, each containing individual antimicrobial agents.

Antimicrobial composition for protecting wood


A rotary cylinder for controlling operations of a chuck to be used on a lathe or the like. The rotary cylinder comprises a housing, a cylinder unit, a distributor supporting the cylinder unit in bearings fitted therein, and a seizure detecting system including a detaining mechanism for restraining the distributor from rotation relative to the housing. The seizure detecting system detects seizure between the distributor and the cylinder unit and allows the distributor to rotate relative to the housing. The distributor is capable of being fixedly held on the housing without distorting the bearings supporting the cylinder unit and of being disconnected from the housing when seizure occurs between the distributor and the cylinder unit.

1. Field of the Invention
The present invention relates to a rotary cylinder device for controlling operations of a chuck to be used on a lathe or the like.
2. Description of the Related Art
Generally, a rotary cylinder device is constructed by fitting a piston axially sidably in a cylinder unit, supporting the cylinder unit for rotation in a bearing on a distributor, and fitting the distributor in an annular draining space formed in a housing. A rotary cylinder device disclosed in JP-B-63-41689 (reference 1) has a distributor positioned and held fixedly in place in an annular space with a bolt screwed in a housing so that its tip is pressed against the distributor. Another rotary cylinder device disclosed in JP-A-61-241505 (reference 2) has a distributor held fixedly in place in an annular space with a bolt screwed in a housing so that its free end part is fitted in a radial hole formed in the distributor.
Vibrations may be generated in those prior art rotary cylinder devices if the distributor makes a slight turning movement in a direction opposite to a direction in which the cylinder unit rotates at a high rotational speed. Therefore, the distributor is fastened to the housing with the bolt as mentioned in the references 1 and 2. In the reference 1, the bolt is pressed against a part of the distributor separated from an annular groove, such as an oil passage, formed in the distributor and hence the bolt is pressed unavoidably against a part of the distributor near the bearing. Consequently, it is possible that the bearing is distorted by pressure exerted on the distributor by the bolt. In the reference 2, if foreign matters are caught in the thin annular space between the distributor and the cylinder unit and cause seizure between the distributor and the cylinder unit, the distributor is forced to rotate together with the cylinder unit. Therefore, it is possible that the torque of the cylinder unit is transmitted through the distributor and the bolt to the housing and the housing is forced to rotate together with a high-pressure hose connected thereto.
Seizure between the cylinder unit and the distributor can be known from the excessive rise of load on the spindle motor of a lathe or the like. However, the excessive load that may be produced by seizure between the cylinder unit and the distributor and may be exerted on the spindle motor must be greater than a load corresponding to a cutting force necessary for machining. Therefore, the rotary cylinder device may be damaged seriously and troubles will occur before seizure between the cylinder unit and the distributor is detected.


An optical coherence-domain reflectometry system provides an interferometer driven by a broadband incoherent light source with the device under test connected to one arm of the interferometer and a movable scanning mirror in the other arm providing a reference signal. The mirror moves at a controlled velocity to produce a Doppler shift in the reference signal frequency. The reference signal arm also includes a piezoelectric transducer which modulates the phase of the reference signal at a given frequency, causing a further shift in the reference signal frequency. The interference signal is detected and measured by a polarization diversity receiver. A linear polarizer in the reference signal arm is adjusted to produce equal reference signal powers in each arm of the polarization diversity receiver in the absence of a reflection signal from the test arm. The measured reflectometry signal is substantially independent of the state of polarization of the reflected signal from the device under test.

This invention pertains generally to the field of optical measurements and measuring devices, and more particularly to reflectometers for measuring the characteristics of optical systems.
The traditional method for making reflectometer measurements is known as optical time domain reflectometry (OTDR). This is an important nondestructive technique for analyzing and diagnosing optical systems, and it is particularly useful in the manufacturing, installation and maintenance of optical fiber systems. Briefly, the method consists of injecting a short intense pulse of light into a fiber and measuring the time-dependent backscattering light signal. This measured signal contains information about the location, type and magnitude of discontinuities, defects, and anomalies of the fiber and other factors which affect the light propagation such as temperature, mechanical strain, and electric and magnetic fields. The technique is essentially analogous to radar and sonar ranging techniques, but implemented for electromagnetic radiation at optical frequencies. The value of this technique lies largely in the fact that an optical system can be studied from a single access point, e.g. the input end of an optical fiber. This advantage obviates the necessity for dismantling the system, and it becomes extremely important when one is diagnosing very large systems such as long optical fibers. A review of this technology has been written by Peter Healey in the article entitled "Review of Long Wavelength Single-Mode Optical Fiber Reflectometry Techniques", published in the Journal of Lightwave Technology, Vol. LT-3, No. 4, August 1985, pp. 876-886.
The conventional OTDR technique becomes less useful when it is applied to smaller optical systems because of the limits on the measurement resolution inherent in this technique. The resolution is defined by the length of the injected light pulse. A reduction in this pulse length implies either a reduction in average pulse energy or an increase in peak power, both of which are constrained within certain limits. Furthermore, shorter pulses require greater bandwidths of the pulses, which are also limited for any given system. Typically the resolution obtained with an OTDR measurement is of the order of 10 meters, and in practice, the resolution limit of this technique is approximately 1 meter ["OFDR Diagnostics for Fibre and Integrated-Optic Systems"; S. A. Kingsley and D. E. N. Davies, Electronics Letters, Vol. 21, No. 10, March 1985, pp. 434-435]. Clearly the conventional OTDR method is not useful in analyzing small systems such as integrated-optic circuits, or for high-resolution fiber-optic sensing such as measuring stresses at short intervals along a fiber.
Improved resolution can be obtained by means of a method termed "optical frequency domain reflectometry (OFDR)", or also commonly referred to as FMCW (frequency modulated continuous wave) reflectometry. This method is described in the above-referenced article by Kingsley and Davies, and in the paper entitled "Optical Frequency Domain Reflectometry in Single-Mode Fiber", written by W. Eickhoff and R. Ulrich, published in Applied Physics Letters 39 (9), Nov. 1, 1981, pp. 693-695. This technique consists of injecting a highly monochromatic beam of light into the optical system, varying the frequency slowly with a time-linear sweep and detecting the backscattered signal. This detection is achieved by the heterodyne method, in that the backscattered signal is mixed coherently with the reference input signal. The beat frequency is measured, and gives the position of a reflection point in the fiber. The amplitude of the beat signal also determines the backscattering factor and attenuation factor for the reflected light. The article by Kingsley and Davies, cited above, reports a resolution of about 3 millimeters obtained by this method and estimates that this can be improved to approximately 1 mm with existing technology.
Clearly the OFDR method offers the capability of improved resolution compared to the conventional OTDR technique. Since the OFDR method is a coherent measurement of interference between a backscattering signal and a reference signal it also offers a greater dynamic range and improved signal-to-noise ratio over a standard OTDR measurement of reflected signal power. Since the OFDR method requires only low optical input signal power, the nonlinear effects of optical transmission in the fiber are reduced. However there are also certain drawbacks to the OFDR technique. Not only does the method require a highly monochromatic source, but it is also sensitive to frequency-sweep nonlinearities, and it is limited by the frequency sweep range.
Heterodyne detection has also been used in OTDR systems with very short pulses to achieve resolutions in the micrometer range. Systems of this type are described in a paper by R. P. Novak, H. H. Gilgen and R. P. Salathe entitled "Investigation of Optical Components in Micrometer Range Using an OTDR System With the Balanced Heterodyne Detection", and a paper by P. Beaud, J. Schutz, W. Hodel, H. P. Weber, H. H. Gilgen and R. P. Salathe, entitled "High Resolutional Optical Time Domain Reflectometry for the Investigation of Integrated Optical Devices", published in the IEEE Journal of Lightwave Technology, Vol. 25 (1989), pp. 755-759. For purposes of clarity this technique may be termed "coherent OTDR". These authors report that by using ultrashort pulses and a coherent detection scheme, the OTDR method can achieve resolutions of about 60 .mu.m in air.
Further improvement in resolution has been obtained by another technique known as "optical coherence-domain reflectometry" (OCDR). This method is described in the following three articles:
(1) "Optical Coherence-Domain Reflectometry: A New Optical Evaluation Technique", by Robert C. Youngquist, Sally Carr, and D. E. N. Davies, Optics Letters, Vol. 12, No. 3, March 1987, pp. 158-160; (2) "New Measurement System for Fault Location in Optical Waveguide Devices Based on an Interferometric Technique", K. Takada, I. Yokohama, K. Chida, and J. Noda, Applied Optics, Vol. 26, No. 9, May 1, 1987, pp. 1603-1606; (3) "Guided-Wave Reflectometry with Micrometer Resolution", B. L. Danielson and C. D. Whittenberg, Applied Optics, Vol. 26, No. 14, Jul. 15, 1987, pp. 2836-2842. The OCDR method differs from the coherent OTDR technique in that instead of a pulsed light source one uses a broadband continuous-wave source with a short coherence length. The source beam enters an interferometer in which one arm has a movable mirror, with the reflected light from this mirror providing a reference beam, and the other arm contains the optical system being tested. The interference signal in the coherently mixed reflected light from the two arms is detected by the usual heterodyne method and yields the desired information about the optical system.
In essence, the OCDR technique replaces the beam pulses by the "coherent domains" in a broadband continuous beam, where a domain is defined as a section of the beam in which the light phases are coherently related. The average size of these sections is termed the "coherence length", 1.sub.c, and is of the order: EQU 1.sub.c .about.c/.DELTA..nu., (1)
where c is the speed of light and .DELTA..nu. is the frequency spread of the light source. [Principles of Optics", 4th Edition, M. Born and E. Wolf, Pergamon Press, New York (1970), Section 7.5.8]. The heterodyne detection of the backscattered "domains" is accomplished by the method of "white light interferometry", in which the beam is split into the two arms of an interferometer, reflected by the adjustable mirror and the backscattering site and coherently recombined. This method utilizes the fact that interference fringes will appear in the recombined beam only when the difference in the optical path length between the two arms is less than the coherence length of the beam, 1.sub.c. The OCDR systems described in references (1) and (3) above make use of this principle, and reference (3) shows interferograms of fiber gaps in test systems obtained by scanning the adjustable mirror and measuring the strength of the recombined signal. Reference (1) also describes a modified method in which the mirror in the reference arm oscillates at a controlled frequency and amplitude, causing a time-varying Doppler shift in the reference signal, and the recombined signal is fed into a filtering circuit to detect the beat frequency signal.
Another variation of this technique is illustrated in reference (2), in which the reference arm mirror is at a fixed position and the difference in optical path lengths in the two arms may exceed the coherence length. The combined signal is then introduced into a second Michelson interferometer with two mirrors, one fixed in position and the other being moveable. This moveable mirror is scanned, and the difference in path length between the arms of the second interferometer compensates for the delay between the backscattered and reference signals at discrete positions of the mirror corresponding to the scattering sites. In practice, an oscillating phase variation at a definite frequency is imposed on the signal from the backscattering site by means of a piezoelectric transducer modulator (PZT) in the fiber leading to this site. The output signal from the Michelson interferometer is fed to a lock-in amplifier, which detects the beat frequency signal arising from both the PZT modulation and the Doppler shift caused by the motion of the scanning mirror. This technique has been used to measure irregularities in glass waveguides with a resolution as short as 15 .mu.m ["Characterization of Silica-Based Waveguides with an Interferometric Optical Time-Domain Reflectometry System Using a 1.3-.mu.m-Wavelength Superluminescent Diode", K. Takada, N. Takato, J. Noda, and Y. Noguchi, Optics Letters, Vol. 14, No. 13, Jul. 1, 1989, pp. 706-708].
In short, the OCDR technique offers the capability of high-resolution measurement of optical systems, together with all of the other advantages of coherent reflectrometry. The optical dynamic range obtainable with this technique can exceed 100 dB on the power logarithmic scale, which implies that refractive index discontinuities of 10.sup.-5 producing reflected light of the order of 1 femtowatt can be detected. The fundamental limitation on the resolution is the coherence length of the light source, which can be reduced to a few microns, with a corresponding increase in source bandwidth.
The OCDR, OFDR, and coherent OTDR techniques all share a common problem arising from the polarization properties of the light beam. This problem is based on the fact that interference between two beams of light can only occur when both beams have the same polarization state. More precisely, the interference signal of two light beams is the incoherent sum of the interference signals from the beam components in two orthogonal polarization states. For example, if one beam is linearly polarized in the horizontal direction and the other beam is linearly polarized in the vertical direction, no interference will occur. Ideally, of course, when the entering beam is split into the two arms of an interferometer, and reflected and coherently recombined, the beam polarization is unchanged. Reference (2), discussed above, includes a polarizer and analyzer mutually aligned at the entrance and exit fibers of the first interferometer to enforce this requirement. In practice, any real fiber will cause a certain amount of distortion of the polarization of the light traveling through it. Furthermore this polarization distortion may be time-dependent. Polarization noise and cross-talk in a fiber may be caused by internal and external perturbations from mechanical, thermal and electromagnetic effects, and can produce fading or reduced visibility of the observed fringes in an interferogram. In addition the signature of a given backscattering site can be complicated by the group delay differences between two polarization eigenmodes in a birefringent fiber.
This problem has been recognized by those skilled in the art and has been mentioned repeatedly in the literature; see for example: "Fading Rates in Coherent OTDR", P. Healey, Electronic Letters, Vol. 20, No. 11, May 24, 1984, pp. 443-444; "Birefringence and Polarization Dispersion Measurements in High-Birefringence Single-Mode Fibers", M. Monerie and F. Alard, Electronics Letters, Vol. 23, p. 198 (1987). In fact, OCDR and interferometric techniques have been widely used to measure polarization distortion in fibers; see for example: "Measurement of Spatial Distribution of Mode Coupling in Birefringent Polarization-Maintaining Fiber with New Detection Scheme", K. Takada, J. Noda and K. Okamoto, Optics Letters, Vol. 11, No. 10, October 1986, pp. 680-682; "Chromatic Dispersion Characterization in Short Single-Mode Fibers by Spectral Scanning of Phase Difference in a Michelson Interferometer", J. Pelayo, J. Paniello, and F. Villuendas, Journal of Lightwave Technology, Vol. 6, No. 12, December 1988, pp. 1861-1865; "Three Ways to Implement Interferencial Techniques: Application to Measurements of Chromatic Dispersion, Birefringence, and Nonlinear Susceptibilities", P.-L. Francois, M. Monerie, C. Vassallo, Y. Durteste, and F. R. Alard, Journal of Lightwave Technology, Vol. 7, No. 3, March 1989, pp. 500-513; "Measurement of Mode Couplings and Extinction Ratios in Polarization-Maintaining Fibers", M. Tsubokawa, T. Higashi, and Y. Sasaki, Journal of Lightwave Technology, Vol. 7, No. 1, January 1989, pp. 45-50.
An extensive discussion of this problem is given in the article: "Polarization-State Control Schemes for Heterodyne or Homodyne Optical Fiber Communications", T. Okoshi, Journal of Lightwave Technology, Vol. LT-3. No. 6, December 1985, pp. 1232-1237. In this paper it is acknowledged that the use of polarization-maintaining fibers is theoretically a complete solution to the problem, but this solution is unsatisfactory for practical reasons. The author mentions two alternative approaches, namely a) the use of a polarization-state control device which matches the reference signal polarization with that of the test signal, and b) the use of a polarization diversity receiver (PDR) in which two orthogonal polarization components of the combined signal are detected separately and added later after an appropriate phase compensation. The author goes on to discuss various schemes for implementing approach a), with no further mention of approach b). Several problems are described that arise in one or more of these polarization-state control schemes, namely:
a) Insertion Loss. The insertion of a polarization control device may attenuate the desired reflectometry signal.
b) Endlessness in Control. The polarization-state distortion of the system may fluctuate over an unknown range, and therefore a control device of limited range may require "resetting" periodically.
c) Temporal Response. The polarization state may fluctuate with unknown rapidity. Manual control of the device may be inadequate. An automatic control feedback scheme may have too long a response time to track these fluctuations accurately.
d) Presence or Absence of Mechanical Fatigue. All schemes that include movement of mechanical components in response to polarization fluctuations suffer from the possibility of mechanical fatigue.
Each of the techniques described in the Okoshi article has at least one of the above drawbacks. The conclusion of this paper is that none of the schemes considered are fully satisfactory, and further efforts are required.
The above Okoshi paper refers only to the use of PDR technology in the context of heterodyne or homodyne optical fiber communications. The PDR is an optical heterodyne receiver that detects signals having an arbitrary polarization state, and is described in the article: "Polarization Independent Coherent Optical Receiver", B. Glance, Journal of Lightwave Technology, Vol. LT-5. No. 2, February 1987, pp. 274-276. Further discussions of the PDR technique are presented in the following articles: "Polarisation-Insensitive Operation of Coherent FSK Transmission System Using Polarisation Diversity", S. Ryu, S. Yamamoto, and K. Mochizuki, Electronics Letters, Vol. 23, No. 25, Dec. 3, 1987, pp. 1382-1384; "First Sea Trial of FSK Heterodyne Optical Transmission System Using Polarisation Diversity", S. Ryu, S. Yamamoto, Y. Namihira, K. Mochizuki and H. Wakabayashi, Electronics Letters, Vol. 24, No. 7, Mar. 31, 1988, pp. 399-400; "New Phase and Polarization-Insensitive Receivers for Coherent Optical Fibre Communication Systems", N. Singh, H. M. Gupta, and V. K. Jain, Optical and Quantum Electronics, Vol. 21, (1989), pp. 343-346; "Adaptive Polarisation Diversity Receiver Configuration for Coherent Optical Fibre Communications", A. D. Kersey, M. J. Marrone, and A. Dandridge, Electronics Letters, Vol. 25, No. 4, Feb. 16, 1989, pp. 275- 277. These articles all discuss the use of PDR techniques for heterodyne reception of optical signals to eliminate the fiber polarization distortion problem. No suggestion is made of this PDR technique as a possible means of dealing with the polarization distortion of optical fibers in coherent reflectometry.
To summarize the technological state of the art, it is known that improved resolution and signal-to-noise ratios in reflectometry systems can be obtained by using coherent detection schemes; that is, optical interferometry systems in which the reflection signal is coherently mixed with a reference signal and the resulting interference signal is detected. Furthermore the optimal coherent detection scheme from the standpoint of resolution is the OCDR, in which the resolution is determined by the coherence length of the light source. This resolution can be made very small by using a broadband source.
It is also known that this coherent detection scheme, like all optical coherent detection schemes, depends on the polarization stability of the optical transmission through the system. Interference between light beams can only occur with signals having the same state of polarization. Changes in the polarization of signals in one arm of the interferometer, or uncorrelated changes in both arms, will degrade the resulting interference signal. These variations in polarization can arise from many causes, both internal and external in nature. Furthermore with respect to external causes, the variations in beam polarization may be time-dependent, arising from fluctuations in environmental conditions.
The polarization stability problem is not confined to optical coherent reflectometry systems. It occurs also in optical communication systems using coherent detection schemes. In this context solutions have been proposed of two general types: direct polarization controllers and polarization diversity receivers. The PDR systems have been designed specifically for this context.
In the reflectometry situation, one can eliminate part of the polarization stability problem by careful design and fabrication of the interferometer. Polarization-maintaining fibers can be used, and the instrument can be encased in a housing to substantially insulate it from environmental perturbations. This is only a partial solution because in operation the instrument must be connected to the device being tested, presumably through optical fibers or other transmission means, and polarization distortion may occur in these external fibers or signal conduits. Furthermore the system under test may itself produce variations in the polarization of the reflectometry signal at reflection or refraction sites or in the optical conduits within the system. These perturbations may be environmental in origin and may fluctuate with time in an essentially uncontrollable manner. Therefore, in an optical coherent reflectometer there is always a polarization instability problem with respect to the optical signals being transmitted and received in the arm of the interferometer that is connected to the device under test.

Polarization independent optical coherence-domain reflectometry


A molten carbonate electrochemical cell operating at a temperature between 400.degree. and 700.degree. C. is used to remove O.sub.2 in combination with CO.sub.2 from an oxygen/combustibles gas mixture to provide a low temperature measurement of the oxygen content of the gas mixture.

The quantitative measurement of oxygen in the presence of combustibles, such as hydrogen or carbon monoxide, is important.
Traditional gas analysis methods, such as gas chromotography, can be used, but these methods require gas sampling and do not provide the in-situ type of analysis that allows fast control of firing conditions to prevent hazardous conditions. Thus, it is preferred to use an in-situ probe-type sensor for monitoring these potentially explosive conditions.
Conventional electrochemical potential measurements of commercially available probe-type solid electrolyte sensors are undesirable for this gas measuring application in that such devices operate at temperatures, i.e. 800.degree.-1200.degree. C., at which undesirable reactions occur between the oxygen and fuel constituents of a gas mixture.

Sensor for oxygen-combustibles gas mixtures


A sun tracking solar energy collector system comprising a plurality of light focusing elements disposed side by side in the form of a surface array, providing a linear array of foci; and a metallic heat exchanger tube having externally a high absorbtivity, low reflectivity coating containing a working fluid such as water, air, hydrogen or helium, to which a substantial portion of the energy in the focused light is imparted. The system includes an insulator tube external to the heat exchanger and providing small apertures covered by glass to allow the light focused by each focusing element to enter the interior of the insulator tube, where the light may impinge directly on the heat exchanger tube or on solar cells attached to the heat exchanger and facing the apertures, for conversion of a portion of the focused light energy directly into electricity, while the greater portion of the energy focused through the apertures ends up as heat through the heat exchanger tube into the working fluid, capable of raising its temperature to a desirable temperature. A highly reflective internal surface of the insulator tube serves to reflect toward the heat exchanger radiation reaching it from the solar cells and the heat exchanger, so that with the reflective internal surface being much larger than the surface covered by the apertures a very small percentage of the radiated energy is allowed to escape to space through the apertures. A vacuum maintained between the heat exchanger and the external insulator tube serves to minimize conductive losses.

1. Field of the Invention
This invention relates in general to solar energy collectors for capturing solar energy falling over a surface area, in terms of heat, raising the temperature of a fluid, and particularly to a sun tracking solar energy collector system means for increasing the temperature of the fluid and the efficiency of solar energy capture per unit of area using focussing means, solar tracking means, solar cells and an internal type heat exchanger means.
2. Description of the Prior Art and of Optimizing Factors
There has been a number of devices for capturing and utilizing heat energy from the sunlight. One type of such devices is the passive non tracking solar energy collecting panels providing in effect heat exchanging means between a highly light absorbing coating and water which is used for heating during the winter and for faucet hot water the year around. Coatings with much higher absorbitivity than emissivity in the range of the solar spectrum have been developed. The principle of what is commonly known as the "hot house effect" whereby visible light is easily transmitted through a transparent sheet, such as glass or acrylic plastic, imparting heat energy onto the absorbing surface at relatively low temperatures, so that the surface then can only radiate in the infrared spectrum which is only partially transmitted through said sheet, is beneficially used to retain the captured heat. The main drawbacks of this type of solar collecting devices are:
1. Lacking sun tracking the surface where the light collecting device is installed is inefficiently used due to the cosine law, capturing only a small portion of its potential energy capture.
2. The temperature at which the water can be raised is relatively low (about 145.degree. F.). While low temperature is useful for heating and for hot water, it cannot be used efficiently for the generation of electricity or to provide for air-conditioning through an absorption type refrigeration unit.
3. Despite the "hot house effect" a considerable amount of the captured heat is being re-radiated into space, or lost through conduction to the outside air.
4. Defining a price quality factor as the yearly dollar benefit derived by the device, divided by the overall cost of the installation, it has been found that such factor is relatively low for this type of solar collectors.
A second type of solar collecting devices may be referred to as line focus solar energy collecting devices which use optical means such as Fresnel lenses or cylindrical paraboloidal reflectors to concentrate the sun light along a narrow focal line. This type may or may not include sun tracking means.
The main benefit of the line focus solar collectors is that they provide sufficient light concentration to heat working fluid such as water to an intermediate temperature such as between 200 and 300.degree. F. Such water temperatures are capable of efficiently providing heat to an absorption type air conditioning system besides providing heating during the winter and hot water.
The main drawback of the line focus solar collectors is the relatively high percentage or radiation losses, as a relatively high percentage of the heat exchanger receiving the radiation is exposed to radiate back into space. Difficulties also exist in keeping a vacuum between an inner heat exchanger and an outer shield when a slot along the outer shield must remain transparent for the solar radiation to enter. Attempting to cover the slot with a transparent substance such as glass while keeping the glass sealed surrounding a metallic inner heat exchanger, and at a wide range of temperatures, while maintaining a vacuum between the glass shield and the metallic heat exchanger.
A third type of solar collecting devices may be referred to as superimposed focusing collectors providing focusing of a multiplicity of sun tracking reflectors commonly referred to as heliostats, on to same area of a heat exchanger, where substantially high temperature can be sustained.
The main advantage of the superimproved focussing solar collectors in that they can gather substantial amounts of solar energy per day, measured in megawatt hrs. per day. A drawback is that only a small portion of the heliostats is contributing efficiently to the common heat exchanger at any time. Also because of the high temperatures involved at the heat exchanger radiation losses can be considerable. This type of system can be acceptable in areas with high intensity of sun-light and inexpensive land.
While the solar energy now falling over the roofs of houses and industrial buildings is almost entirely being wasted, as the price of oil will increase, the value of this energy will also increase. Solar energy collectors which may appear to provide a benefit in terms of hot water to a homeowner today may be determined to be wasteful a few years from now when the cost of thermal energy will have substantially been increased.
It should be noted that it is not only the number of BTU's collected per year per unit area of surface that counts but also the temperature at which these BTU's are counted. The higher the temperature of the working fluid the higher the value of the energy because the heat in the hotter working fluid can be converted into more valuable forms of energy such as electricity, at a higher efficiency. From Carnot's cycle considerations the maximum thermal efficiency possible in a heat engine is EQU nc=1-T.sub.L /T.sub.H ( 1)
Where T.sub.H and T.sub.L are the high and low temperatures between which the engine operates, expressed as absolute temperatures. If T.sub.L is taken to be the ambient temperature, which is usually the case, the efficiency n.sub.c deteriorates as T.sub.H is approaching T.sub.L. While n.sub.c is unattainable in practical engines, the expression (1-T.sub.L /T.sub.H) turns out to be a controlling factor in the expression of the efficiency of heat engines. It is for this reason that BTU's at relatively low temperature gases such as the gases from the flute of oil burners and the exhaust of the automobiles are allowed to excape because the temperature of such gases is too low compared to the high temperature of the system.
Another desirable feature of a solar energy collection system is the evenness of energy output during a normal sunny day. The smaller the variation of energy output during the day the less energy storage will be required by the system.
On these basis it will be useful that a qualification factor "q" of a solar energy collection system be defined in such a way as to include all relevant factors, such as shown in the following equation: EQU q=(1-T.sub.A/ T.sub.H).times.K /(A.times.C.times..sigma.) (2)
Where
T.sub.A is the average absolute ambient Temperature; PA1 T.sub.H is the high temperature of the working fluid; PA1 K is the ratio of the amount of energy retained by the collector divided by the amount of energy incident per unit area at normal incidence; PA1 A is the area of ground or roof utilized by the solar collecting device; PA1 C is total cost in dollars for implementing the system; and PA1 .sigma. is the standard deviation of BTU output per hour per unit area of collector during the 12 sunny hourly intervals, 6 a.m. to 6 p.m. daily. PA1 K is being optimized by the invention's providing means for sun tracking for both daily motion of the sun and the seasonal declination of latitude .+-.23.5.degree.. K is further being optimized by the invention's providing means for minimizing radiation losses. (1-T.sub.A /T.sub.H) is being improved by the invention increasing the temperature of the working fluid through focussing of the solar energy, preferably through lenses; PA1 A is being minimized by the invention by positioning a multiplicity of focussing lenses on a single platform thereby tracking the sun in unison and precluding shading of one lense by another as it usually occurs in other systems during the early morning and late afternoon hours. PA1 .sigma. is being minimized by the sun tracking and by avoiding shading through the single platform principle. PA1 optical focusing means for concentrating sunlight falling on rectangular surface strips of optical focusing elements onto a much smaller area in the vicinity of the focus of the optical focusing means: PA1 a tubular metallic heat exchanger for containing a working fluid such as water or a gas and running along the foci of the optical focusing means thereby transferring the heat received by the concentrated sunlight to the working fluid; PA1 an insulating tube preferably metallic placed around the heat exchanger and presenting a highly reflective internal surface towards the metalic heat exchanger for reflecting back radiation emitted by the heat exchanger; PA1 small circular openings on the insulating tube covered with a transparent material such as glass for allowing the focused sunlight to enter the insulating tube and to reach the heat exchanger, the apertures constituting only a small portion of the total surface of the insulating tube; PA1 a vacuum maintained between the heat exchanger and the insulating tube for lowering conductive heat losses between the heat exchanger and the outside air; and PA1 a solar tracking platform for supporting the solar focusing means, the heat exchanger, and the insulating tube so that the optical axis of the optical focusing means remains substantially alligned with the direction of the sun.

Sun tracking solar energy collector system


A reflective liquid crystal display device including: a first substrate; a second substrate; a liquid crystal layer interposed between the first substrate and the second substrate; electrodes for applying a voltage to the liquid crystal layer; a polarizing plate provided on a side of the liquid crystal layer on which the first substrate is provided; a reflective member provided on a side of the liquid crystal layer on which the second substrate is provided; and an optical compensation member provided between the polarizing plate and the liquid crystal layer, wherein the liquid crystal layer has a twist angle in a range of 220.degree. to 260.degree. and a retardation value of 0.5 .mu.m to 0.8 .mu.m, the optical compensation member has a retardation value in a range of 0.15 .mu.m to 0.38 .mu.m, and an angle .beta. which is formed between a polarization axis direction of the polarizing plate and an alignment direction of liquid crystal molecules in the liquid crystal layer on a side of the polarizing plate, and an angle .gamma. which is formed between an axis direction of a slower optical axis of the optical compensation member and an alignment direction of the liquid crystal molecules, satisfy one of following expressions (A) and (B) when m is an integer: EQU 0.5.beta.+45.degree. m-15.degree..ltoreq..gamma..ltoreq.0.5.beta.+45.degree. m+5.degree.(A) EQU 0.5.beta.+45.degree. m+7.5.degree..ltoreq..gamma..ltoreq.0.5.beta.+45.degree. m+27.5.degree.(B). is disclosed.

1. Field of the Invention
The present invention relates to a liquid crystal display device, and more specifically, to a reflective liquid crystal display device which is used for OA (office automation) apparatuses such as word processors and notebook type personal computers, various image display apparatuses, and apparatuses for playing games.
2. Description of the Related Art
In recent years, the application of a liquid crystal display device (LCD) to a word processor, a lap-top personal computer, a portable television set called a "pocket TV", or the like has been rapidly developed. Conventionally, a twisted nematic (TN) mode and a super-twisted nematic (STN) mode are employed in such an LCD.
In the above-mentioned TN mode, a monochrome display (a black and white display) is conducted by using the optical characteristics of a liquid crystal display device (liquid crystal panel) interposed between a pair of polarizing plates, i.e. the optical rotatory characteristics when no voltage is applied and the optical non-rotatory characteristics when a voltage is applied.
In the STN mode, which is widely used for a display mode of a word processor, a twist angle of liquid crystal layer is set to be in the range of 180.degree. to 270.degree. in a liquid crystal panel of a similar structure to that in the TN mode. According to the STN mode, the twist angle of liquid crystal layer is increased by 90.degree. or more and the setting angle of the polarizing plates is optimized, thereby realizing an electro-optic characteristics with a steep threshold characteristic which reflect the rapid change of the orientation of liquid crystal molecules with an application of a voltage on the change of the birefringence of the liquid crystal layer. Since the STN mode has a steep threshold characteristic, the STN mode is suitable for simple matrix driving.
In the STN mode, the birefringence of the liquid crystal layer causes the background of the display to be colored in yellowish green or dark blue. In order to improve this drawback, an LCD is proposed in which a monochrome display is realized by means of color compensation which is conducted by attaching an optical compensation panel or a phase plate formed by a polymer such as polycarbonate to the liquid crystal panel of the STN mode. An LCD of such a structure, so-called "paper white LCD", is currently on the market. The detailed operational principle in the TN mode and STN mode is already well known in the art and is disclosed in "Liquid Crystal Device Handbook", Ed. by Japan Society for Promotion of Science, Committee 142, 1989, pp. 329-352.
In such an LCD of the TN or STN mode, however, if the LCD is used as a reflective LCD, the obtained display is undesirably darkened, because two polarizing plates interposing a liquid crystal panel are used. In order to solve the problem, reflective LCDs of the STN mode with a single polarizing plate are proposed in Japanese Laid-Open Patent Publication Nos. 4-97121 and 4-289818.
However, in the proposed LCDs mentioned above, none of the means to solve the following problems is mentioned: the prevention of the coloring of the displayed color during a gray-scale display, the retardation value of the liquid crystal layer, the retardation value of the optical compensation plate (phase plate), and the related position of the polarizing plate and the optical compensation plate. Consequently, in such LCDs, the prevention of the coloring of the displayed color cannot be realized during a gray-scale display.

Reflective liquid crystal display device having a compensator with a retardation value between 0.15 .mu.m and 0.38 .mu.m and a single polarizer