The present invention relates to a polymerizable composition, comprising a) at least one compound of formula (I)

The present invention relates to radically polymerizable compositions, containing at least one light stabilizer with an ethylenically unsaturated group and to oligomers, polymers, cooligomers or copolymers having low polydispersity Mw/Mn, which are prepared by controlled radical polymerization from the polymerizable composition. Further aspects of the invention are a process for their preparation, their use as light or heat stabilizers for organic materials, particularly for synthetic polymers, paints, enamels or varnishes and the organic materials thus stabilized.
The stabilization of polymers with light/heat stabilizers such as 2,2,6,6-tetramethylpiperidine derivatives, hydroxy-benzophenones, hydroxy-benzotriazoles and hydroxy-phenyl-s-triazines is well known. It is also known to prepare and to use oligomeric or polymeric light stabilizers of the above mentioned classes for the stabilization of polymers. This is for example described in U.S. Pat. No. 4,294,949 and in U.S. Pat. No. 4,785,063. These polymeric light stabilizers are all prepared by a conventional free radical polymerization process.
However polymers or copolymers prepared by free radical polymerization processes inherently have broad molecular weight distributions or polydispersities which are generally higher than about four. One reason for this is that most of the free radical initiators have half lives that are relatively long, ranging from several minutes to many hours, and thus the polymeric chains are not all initiated at the same time and the initiators provide growing chains of various lengths at any time during the polymerization process.
Due to the broad molecular weight distribution and high molecular weights of the polymeric light stabilizers problems arise when they are incorporated into paints, coatings, or thermoplastic polymers. They cause for example a strong viscosity increase in paints and coatings, which is undesirable for the paint""s application, in particular for the spray application of automotive coatings. In thermoplastic polymers compatibility problems may arise particularly with the high molecular weight portion of the polymeric light stabilizers. For these reasons polymeric light stabilizers having a low polydispersity are desirable for many applications.
The light stabilizers of the present invention are polymeric resin products having low polydispersity. The polymerization process proceeds with good monomer to polymer conversion efficiency, thus being also feasible on an industrial scale. In particular, this invention relates to stable free radical-mediated polymerization processes or to a, free radical initiated polymerization process by the ATRP (Atom Transfer Radical Polymerization) method which provide homopolymers, alternate-, gradient- or random copolymers, block copolymers or multiblock copolymers of different classes of light stabilizers.
The so made polymers or copolymers are highly compatible with thermoplastic polymers and thermosetting coatings. They are very efficient light/heat stabilizers either when used alone or in combination with other known stabilizers. Due to their low polydispersity they are easy to incorporate into other polymers, without for example significantly increasing their viscosity or melting properties.
One subject of the present invention is a polymerizable composition, comprising a) at least one compound of formula (I)
(RG)xe2x80x94Axe2x80x94(Stab)xe2x80x83xe2x80x83(I),
wherein
(Stab) is a light stabilizer radical selected from the group consisting of sterically hindered amines, hydroxyphenyl-s-triazines, hydroxyphenyl-benzotriazols and o-hydroxy-benzophenones; A is a spacer group or a direct bond; and
(RG) is a group containing at least one ethylenically unsaturated functional group; and either b1) a compound of formula (II)
Yxe2x80x94Xxe2x80x83xe2x80x83(II),
xe2x80x83wherein
X represents a group having at least one carbon atom and is such that the free radical derived from X is capable of initiating polymerization and
Y represents a group being such that the free radical Yxc2x7 derived from it forms a stable free radical; or b2) a stable free radical Yxc2x7 and a free radical source from which a radical is formed capable of initiating polymerization; or b3) a compound of formula (III)
xe2x80x83and a catalytically effective amount of an oxidizable transition metal complex catalyst, wherein
p represents a number greater than zero and defines the number of initiator fragments;
q represents a number greater than zero;
[In] represents a radically transferable atom or group capable of initiating polymerization and -[Hal] represents a leaving group; and optionally c) one or more ethylenically unsaturated monomers or oligomers different from those of formula (I).
The sterically hindered amines are preferably selected from the class of piperidines, piperazinones, piperazindiones or morpholinones.
Preferably component a) of formula (I) is a compound of formulae (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii) or (Ij)
W is O, or NR110;
A is a direct bond, xe2x80x94(C2-C12)alkylene-Wxe2x80x94, xe2x80x94(C3-C12)alkenylene-Wxe2x80x94, xe2x80x94CH2xe2x80x94HC(OH)xe2x80x94CH2xe2x80x94Wxe2x80x94, xe2x80x94(C3-C12)alkinylene-Wxe2x80x94, (C5-C12)cycloalkylene-Wxe2x80x94, xe2x80x94(C2-C12)alkylene-Wxe2x80x94 interrupted by at least one oxygen or nitrogen atom or a group xe2x80x94CH2xe2x80x94CHR110xe2x80x94Wxe2x80x94, a group xe2x80x94CHR111xe2x80x94COOP wherein P is xe2x80x94(CH2xe2x80x94HCR112)nxe2x80x94 or a group xe2x80x94CH2xe2x80x94HC(OH)xe2x80x94CH2xe2x80x94, wherein R110, R111, R112 and n are as defined below;
R110 is H or methyl R102 is hydrogen, OH, C1-C18alkyl, C3-C8alkenyl, C3-C8alkynyl; C7-C12aralkyl, C1-C18alkanoyl, C3-C18alkenoyl, C1-C18alkanoyloxy, glycidyl, C1-C18alkoxy, C5-C12cycloalkyl, C5-C12cycloalkoxy or a group xe2x80x94CH2CHR110(OH);
R103 is H, OH, NH2, C1-C18alkoxy, C1-C18alkanoyloxy, C6-C18aryloyloxy, C1-C18alkanoylamino, C1-C18alkylamino, C1-C18alkylamino, benzyloxy or together with the linking carbon atom forms a C5-C6cycloalkyl radical or a C5-C6heterocycloalkyl radical containing one or two oxygen or nitrogen atoms;
R104, R105, R106, R107 are independently C1-C8alkyl or C5-C12cyloalkyl, or R104 and R105 and/or R106 and R107 together with the carbon atom to which they are attached form-a C5-C12cycloalkyl group;
R108 and R109 independently are H, C1-C8alkyl or phenyl;
R110 is hydrogen, C1-C18alkyl or phenyl;
R111 is hydrogen or C1-C12alkyl;
R112 is hydrogen or methyl;
R201 and R202 are independently H, OH, CN, C1-C18alkyl, C1-C18alkoxy, halogen, C1-C18alkanoyl, C1-C18alkanoyloxy, C1-C18alkanoylamino, or phenyl which is unsubstituted or substituted with halogen, OH, CN, NO2, C1-C18alkyl, C1-C18alkoxy or a group xe2x80x94Oxe2x80x94CH2xe2x80x94HC(OH)xe2x80x94CH2xe2x80x94OR206;
R203 and R204 are independently H, OH, CN, C1-C18alkyl, C1-C18alkoxy, halogen, C1-C18alkanoyl, C1-C18alkanoyloxy, C1-C18alkanoylamino, or phenyl which is unsubstituted or substituted with halogen, OH, CN, NO2, C1-C18alkyl, C1-C18alkoxy or a group xe2x80x94Oxe2x80x94CH2xe2x80x94HC(OH)xe2x80x94CH2xe2x80x94OR206 with the proviso that at least one of both is OH;
R205 is H, halogen, phenyl, C1-C18alkyl, C5-C12cycloalkyl, C7-C12aralkyl or a group xe2x80x94SR208, xe2x80x94SO2R208, xe2x80x94COOR208 or PO(OR208)2;
R206 is C1-C18alkyl, C3-C18alkyl interrupted by at least one oxygen atom, phenyl which is unsubstituted or substituted with halogen, OH, CN, NO2, C1-C18alkyl, C1-C18alkoxy, C5-C6cycloalkyl which is unsubstituted or substituted by C1-C4alkyl or a group xe2x80x94C(O)R207;
R207 C1-C18alkyl or phenyl which is unsubstituted or substituted with halogen, OH, CN, NO2, C1-C18alkyl or C1-C18alkoxy;
R208 is C1-C18alkyl, C5-C6cycloalkyl or phenyl;
R209 is H, halogen, phenyl, C1-C18alkyl, C5-C12cycloalkyl, C7-C12aralkyl or a group xe2x80x94SR208, xe2x80x94SO2R208, xe2x80x94COOR208 or PO(OR208)2;
n is a number from 0 to 12, and
k is a number from 0 to 12.
Preferably R108 and R109 are hydrogen and the other substituents are as defined above.
Preferably R104, R105, R106 and R107 are methyl and the other substituents are as defined above.
Preferably A is a direct bond, xe2x80x94(C2-C6)alkylene-Wxe2x80x94, xe2x80x94(C2-C12)alkylene-Wxe2x80x94 interrupted by at least one oxygen or nitrogen atom or a group xe2x80x94CH2xe2x80x94CHCH3xe2x80x94Wxe2x80x94.
W is preferably an oxygen atom.
R102 is preferably hydrogen, C1-C8alkyl, allyl, benzyl, C1-C8alkanoy), C1-C8alkanoyloxy, C1-C8alkoxy or cyclohexyloxy.
Preferably R103 is H, C1-C8alkoxy, C1-C8alkanoyloxy, benzyloxy, C1-C8alkylamino, C1-C8dialkylamino or C1-C8alkanoylamino.
R201, R202, R203 and R204 are independently H, C1-C8alkyl, OH, C1-C8alkoxy, phenyl or halogen, with the proviso that at least one of R203 or R204 is OH.
Preferably R205 is hydrogen, halogen or C1-C8alkyl.
Preferably R206 is C1-C4alkyl or phenyl.
R207 is preferably C1-C4alkyl or phenyl which is unsubstituted or substituted with C1-C18alkoxy;
R208 is pereferably C1-C4alkyl or phenyl;
Preferably n is a number from 2-6 and k is a number from 0-2.
Preferably the compound of formula (I) is a compound of formulae (Ia), (Ic), (Id), (If), (Ig), (Ii) or I(j), more preferably of formulae (Ia), (If), (Ig) or (Ii).
Preferred is a composition, wherein in the compound of formula (Ia), A is a direct bond, C2-C6alkylene or C2-C6alkylene interrupted by at least one oxygen or nitrogen atom; RG is a group
W is an oxygen atom;
R101 is H or methyl
R102 is H, C1-C4alkyl, allyl, benzyl, C1-C6alkoxy, cyclohexyloxy, acetyl or acryloyl;
R104-R107 are methyl and
R108 and R109 are hydrogen.
Particularly preferred is a composition, wherein in the compound of formula (Ia), A is a direct bond; W is an oxygen atom; RG is a group
R101 is H or methyl; R102 is H or C1-C4alkyl; R104-R107 are methyl; and R108 and R109 are hydrogen.
Also preferred is a composition, wherein in the compounds of formulae (If), (Ig) or (Ii)
A is a direct bond, C2-C6alkylene or C2-C6alkylene interrupted by at least one oxygen or nitrogen atom
W is an oxygen atom;
RG is a group
R101 is H or methyl;
R201 and R202 are independently H, C1-C8alkyl, phenyl or OH;
R203 and R204 are independently H, C1-C8alkyl, phenyl or OH with the proviso that at least one of both is OH;
R205 is H, C1-C8alkyl or xcex1-cumyl;
R209 is H or Cl;
and k is a number from 1 to 8.
Particularly preferred is a composition, wherein in the compound of formula (Ii)
A is a direct bond
W is an oxygen atom;
RG is a group
R101 is H or methyl;
R205 is H C1-C8alkyl, phenyl or xcex1-cumyl;
R209 is H or Cl and
k is a number from 1 to 8.
The alkyl radicals in the various substituents may be linear or branched. Examples of alkyl containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as for example propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl oder n-4-octadecenyl.
Preferred is alkenyl with 3 bis 12, particularly preferred with 3 to 8 carbon atoms. C3-C8alkenyl can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, or 4-tert-butyl-2-butenyl.
Alkinyl with 3 to 18 is a linear or branched radical as for example propinyl (xe2x80x94CH2xe2x80x94Cxe2x89xa1CH), 2-butinyl, 3-butinyl, n-2-octinyl, oder n-2-octadecinyl. Preferred is alkinyl with 3 to 12, particularly preferred with 3 to 8 carbon atoms. C3-C8alkynyl is most preferably propargyl.
Examples of C5-C12cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Preferred are cycloheptyl and cyclohexyl.
Examples of alkylene containing 1 to 18 carbon atoms are methylene, ethylene, propylene, isopropylene, butylene, 2-butylene, isobutylene, t-butylene, pentylene, 2-pentylene, hexylene, heptylene, octylene, 2-ethylhexylene, t-octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, hexadecylene and octadecylene.
C2-C18alkylene interrupted by at least one O atom is for example xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94 or xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94. It is preferably derived from polyethlene glycol. A general description is xe2x80x94((CH2)axe2x80x94O)bxe2x80x94/CH2xe2x80x94, wherein a is a number from 1 to 6 and b is a number from 2 to 10.
Alkenylene with 3 to 18 carbon atoms is a linear or branched radical as for example propenylene, 2-butenylene, 3-butenylene, isobutenylene, n-2,4-pentadienylene, 3-methyl-2-butenylene, n-2-octenylene, n-2-dodecenylene, iso-dodecenylene, n-2-octadecenylene or n-4-octadecenylene.
Alkinylene with 3 to 18 is a linear or branched radical as for example propinylene, 2-butinylene, 3-butinylene, n-2-octinylene, or n-2-octadecinylene. C7-C9phenylalkyl is benzyl, phenylethyl or phenylpropyl, especially benzyl.
C1-C8alkanoyl is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl and C3-C5alkenoyl is in particular acryloyl.
C1-C18alkanoyloxy is, for example, formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy and stearoyloxy.
C5-C7cycloalkylene is typically, cyclopentylene, methylcyclopentylene, dimethylcyclopentylene, cyclohexylene, methylcyclohexylene or cyclopentylene.
Halogen is Fluorine, Chlorine, Bromine or Iodine, preferably Chlorine or Bromine.
In the compounds according to formula (Ib) R103 may form together with the linking carbon atom a C5-C6cycloalkyl radical or a C5-C6heterocycloalkyl radical containing one or two oxygen or nitrogen atoms. Typical examples are derived from
50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane
51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane
52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane
53) 9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5.5]undecane
54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane
55) 2,2,6,6-tetramethylpiperidine-4-spiro-2xe2x80x2-(1xe2x80x2,3xe2x80x2-dioxane)-5xe2x80x2-spiro-5xe2x80x3-(1xe2x80x3,3xe2x80x3-dioxane-2xe2x80x3-spiro-4xe2x80x2xe2x80x3-(2xe2x80x2xe2x80x3,2xe2x80x2xe2x80x3,6xe2x80x2xe2x80x3,6xe2x80x2xe2x80x3-tetramethylpiperidine) or from
56) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione
57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione
58) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione
59) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione
60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione
61) 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[220.127.116.11]heneicosane
64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4.5]decane and preferably:
65) 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione
The composition may contain additional ethylenically unsaturated monomers or oligomers as component c).
Preferably the ethylenically unsaturated monomer or oligomer is selected from the group consisting of styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, (alkyl)acrylic acid anhydrides, acrylonitrile, (alkyl)acrylic acid salts, (alkyl)acrylic esters or (alkyl)acrylamides.
More preferably the ethylenically unsaturated monomer is i-butylene, styrene, xcex1-methyl styrene, p-methyl styrene or a compound of formula CH2xe2x95x90C(Ra)xe2x80x94(Cxe2x95x90Z)xe2x80x94Rb, wherein Ra is hydrogen or C1-C4alkyl, Rb is NH2, Oxe2x88x92(Me+), glycidyl, unsubstituted C1-C18alkoxy, C1-C18alkoxy interrupted by at least one N and/or O atom, or hydroxy-substituted C1-C18alkoxy, C1-C18alkoxy interrupted by at least one N and/or O atom, unsubstituted C1-C18alkylamino, di(C1-C18alkyl)amino; hydroxy-substituted C1-C18alkylamino or hydroxy-substituted di(C1-C18alkyl)amino, xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94N(CH3)2 or xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94N+H(CH3)2 Anxe2x88x92;
Anxe2x88x92 is a anion of a monovalent organic or inorganic acid;
Me is amonovalent metal atom, NH4+ or HN+(C1-C4alkyl)3; and
Z is oxygen or sulfur.
More preferably the ethylenically unsaturated monomer is styrene, xcex1-methyl styrene, p-methyl styrene or a compound of formula CH2xe2x95x90C(Ra)xe2x80x94(Cxe2x95x90Z)Rb, wherein Ra, is hydrogen or C1-C4alkyl, Rb is NH2, Oxe2x88x92(Me+), glycidyl, unsubstituted C1-C18alkoxy or hydroxy-substituted C1-C18alkyloxy, unsubstituted C1-C18alkylamino, di(C1-C18alkyl)amino, hydroxy-substituted C1-C18alkylamino or hydroxy-substituted di(C1-C18alkyl)amino;
Me is a monovalent metal atom
Z is oxygen or sulfur.
Examples of monovalent metal atoms are Li, Na, K.
Examples of the anion Anxe2x88x92 of a monovalent organic or inorganic acid are C1-C18carbonic acid anions, the anions of HClO4, HCl or HBr.
Particularly preferred are monomers wherein Ra is hydrogen or methyl, Rb is NH2, gycidyl, unsubstituted or with hydroxy substituted C1-C4alkoxy, unsubstituted C1-C4alkylamino, di(C1-C4alkyl)amino, hydroxy-substituted C1-C4alkylamino or hydroxy-substituted di(C1-C4alkyl)amino; and
Z is oxygen.
Most preferably the ethylenically unsaturated monomer is methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert. butylacrylate, hydroxyethylacrylate, hydroxypropylbutylacrylate, dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylates, acrylonitrile, acrylamide or methacrylamide.
Suitable compounds of formula (II)
Yxe2x80x94Xxe2x80x83xe2x80x83(II),
free radicals Xxc2x7 and stable free radicals Yxc2x7 are known. Stable free radicals having a structural element
are for example disclosed in EP-A-621 878.
Further examples such as
are given in WO 96/24620.
Another suitable stable free radical, 1,3,5,5-Tetraphenyl-1,2,4-triazolin-2-yl, has been described by D. Colombani, M. Steenbock, M. Klapper, K. Mxc3xcllen in Macromol. Rapid. Commun. 18, 243-251 (1997). Further suitable compounds and their preparation are given in WO 99/03894, GB 2 335 190 and in PCT/EP 99/05377.
Initiator/regulator compounds of formula (II) containing a structural element
are in principal known. Suitable compounds and their manufacture are for example described in U.S. Pat. No. 4,581,429, U.S. Pat. No. 5,721,320, U.S. Pat. No. 5,627,248, WO 98/13392, WO 98/30601 or in WO 98/44008.
The composition comprises preferably as component b1) a compound of formula (II)
Yxe2x80x94Xxe2x80x83xe2x80x83(II),
which contains a structural element
wherein the nitrogen atom is part of a cyclic ring system or is substituted to form a acyclic structure.
A preferred acyclic structure is, wherein the compound containing a structural element
is of formula (XXa), (XXb) or (XXc)
wherein
Y1 is O or CH2;
Q1 is O or NR40, wherein R40 is hydrogen or C1-C18alkyl;
R21 is tertiary C4-C18alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42 wherein R41 is hydrogen, a alkali metal atom or C1-C18alkyl and R42 is C1-C18alkyl; or
R21 is C5-C12cycloalkyl, C5-C12cycloalkyl which is interrupted by at least one O or N atom, a polycyclic alkyl radical or a polycyclic alkyl radical which is interrupted by at least one O or N atom;
R22 and R23 are independently C1-C18alkyl, benzyl, C5-C12cycloalkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42 or together with the carbon atom form a C5-C12cycloalkyl ring;
if Y1 is O, R24 and R32 are OH, O(alkali-metal) C1-C18alkoxy, benzyloxy, NR43R44, wherein R43 and R44 are independently from each other hydrogen, C1-C18alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42;
if Y1 is CH2, R24 is OH, C1-C18alkoxy, benzyloxy, Oxe2x80x94C(O)xe2x80x94(C1-C18)alkyl or NR43R44;
R32 are a group C(O)R45, wherein R45 is OH, C1-C18alkoxy, benzyloxy, NR43R44, wherein R43 and R44 are independently from each other hydrogen, C1-C18alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42;
R25, R26, R27 and R28 are independently of each other C1-C18alkyl, C5-C12cycloalykyl or phenyl; or
R25 and R26 and/or R27 and R28 together with the carbon atom form a C5-C12cycloalkyl ring;
R29 and R30 are independently of each other hydrogen, C1-C18alkylcarbonyl, benzoyl, C1-C18alkyl, C5-C12cycloalkyl, C5-C12cycloalkyl which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42;
R31, is C1-C18alkylcarbonyl, benzoyl, C1-C18alkyl, C5-C12cycloalkyl, C5-C12cycloalkyl which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42; and
X represents a group having at least one carbon atom and is such that the free radical Xxc2x7 derived from X is capable of initiating polymerization of ethylenically unsaturated monomers.
Examples for the different substituents have been already given.
Typical examples of suitable compounds are given in Table 1. These compounds and there preparation is described in PCT/EP 99/05377.
Other suitable compounds with symmetrical substitution pattern are derived from nitroso compounds or nitrons and are described in WO 99/03894. Typical examples are given in Table 2. The nitroso and nitrone compounds can also be used as in situ precursors to form the compounds of Table 2 simultaneously to the polymerization step. This is described in WO 99/03894.
Preferably the initiator/regulator compounds form a cyclic structure
which may be a 5, 6, 7 or 8 ring system having no hydrogen atom in xcex1-position to the nitrogen atom and which may contain one additional heteroatom in the ring.
Particularly suitable initiator/regulator compounds are 1-alkoxy-polyalkyl-piperidine derivatives containing a structural element of formula (X)
G1, G2, G3, G4 are independently C1-C6alkyl with the proviso that at least one is not methyl or G1 and G2 or G3 and G4, or G1 and G2 and G3 and G4 together form a C5-C12cycloalkyl group;
G5, G6 independently are H, C1-C18alkyl, phenyl, naphthyl or a group COOC1-C18alkyl and
X represents a group having at least one carbon atom and is such that the free radical Xxc2x7 derived from X is capable of initiating polymerization of ethylenically unsaturated monomers.
These compounds and their preparation are described in GB 2 335 190.
Particularly suitable compounds are listed in Table 3.
Another preferred class of initiators are those of formula (Xa) or (Xb)
R1, R2, R3 and R4 independently of each other are C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by OH, halogen or a group xe2x80x94Oxe2x80x94 C(O)xe2x80x94R5, C2-C18alkyl which is interrupted by at least one O atom and/or NR5 group, C3-C12cycloalkyl or C6-C10aryl or R1 and R2 and/or R3 and R4 together with the linking carbon atom form a C3-C12cycloalkyl radical;
R5, R6 and R7 independently are hydrogen, C1-C18alkyl or C6-C10aryl;
X represents a group having at least one carbon atom and is such that the free radical Xxc2x7 derived from X is capable of initiating polymerization of ethylenically unsaturated monomers;
Z1 is O or NR8;
R8 is hydrogen, OH, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by one or more OH, halogen or a group xe2x80x94Oxe2x80x94C(O)xe2x80x94R5, C2-C18alkyl which is interrupted by at least one O atom and/or NR5 group, C3-C12cycloalkyl or C6-C10aryl, C7-C9phenylalkyl, C5-C10heteroaryl, xe2x80x94C(O)xe2x80x94C1-C18alkyl, xe2x80x94Oxe2x80x94C1-C18alkyl or xe2x80x94COOC1-C18alkyl;
Q is a direct bond or a divalent radical CR9R10, CR9R10xe2x80x94CR11R12, CR9R10CR11R12CR13R14, C(O) or CR9R10C(O), wherein R9, R10, R11, R12, R13 and R14 are independently hydrogen, phenyl or C1-C18alkyl.
The compounds and their preparation are described in WO 98/30601, WO 98/44008 and in the British patent application No. 9923579.8.
Particularly useful are the compounds listed in Table 4, 5 and 6.
Preferably X is selected from the group consisting of
(CH3)2xe2x80x94aryl, C5-C6cycloalkyl)2CCN, (C1-C12alkyl)2CCN, xe2x80x94CH2CHxe2x95x90CH2, (C1-C12)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C12alkyl, (C1-C12)alkyl-CR20xe2x80x94C(O)xe2x80x94(C6-C10aryl, (C1-C12)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C12)alkoxy, (C1-C12)alkyl-CR20xe2x80x94C(O)-phenoxy, (C1-C12)alkyl-CR20xe2x80x94C(O)xe2x80x94N-di(C1-C12)alkyl, (C1-C12)alkyl-CR20xe2x80x94COxe2x80x94NH(C1-C12)alkyl, (C1-C12)alkyl-CR20xe2x80x94COxe2x80x94NH2, xe2x80x94CH2CHxe2x95x90CHxe2x80x94CH3, xe2x80x94CH2xe2x80x94C(CH3)xe2x95x90CH2, xe2x80x94CH2xe2x80x94
wherein
R20 is hydrogen or C1-C12alkyl;
the aryl groups are unsubstituted or substituted with C1-C12alkyl, halogen, C1-C12alkoxy, C1-C12alkylcarbonyl, glycidyloxy, OH, xe2x80x94COOH or xe2x80x94COOC1-C12alkyl.
More preferred are compounds, wherein X is selected from the group consisting of xe2x80x94CH2-phenyl, xe2x80x94CH3CH-phenyl, (CH3)2C-phenyl, (C5-C6cycloalkyl)2CCN, (CH3)2CCN, xe2x80x94CH2CHxe2x95x90CH2, CH3CHxe2x80x94CHxe2x95x90CH2, (C1-C8alkyl)CR20xe2x80x94C(O)-phenyl, (C1-C8)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C8)alkoxy, (C1-C8)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C8)alkyl, (C1-C8)alkyl-CR20xe2x80x94C(O)xe2x80x94N-di(C1-C8)alkyl, (C1-C8)alkyl-CR20xe2x80x94C(O)xe2x80x94NH(C1-C8)alkyl, (C1-C8)alkyl-CR20xe2x80x94C(O)xe2x80x94NH2, wherein R20 is hydrogen or (C1-C8)alkyl.
Particularly preferred are compounds, wherein X is selected from the group consisting of xe2x80x94CH2-phenyl, xe2x80x94CH3CH-phenyl, (CH3)2C-phenyl, (C5-C6cycloalkyl)2CCN, (CH3)2CCN, xe2x80x94CH2CHxe2x95x90CH2, CH3CHxe2x80x94CHxe2x95x90CH2, (C1-C4alkyl)CR20xe2x80x94C(O)-phenyl, (C1-C4)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C4)alkoxy, (C1-C4)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C4)alkyl, (C1-C4)alkyl-CR20xe2x80x94C(O)xe2x80x94N-di(C1-C4)alkyl, (C1-C4)alkyl-CR20xe2x80x94C(O)xe2x80x94NH(C1-C4)alkyl, (C1-C4)alkyl-CR20xe2x80x94C(O)xe2x80x94NH2, wherein R20 is hydrogen or (C1-C4)alkyl.
Another embodiment of the present invention is a composition, wherein component b3) is present as an alternative for b1) or b2).
A suitable component b3) contains a compound of formula (III),
with a radically transferable atom or group xc2x7Hal as is described in WO 96/30421 and WO 98/01480. A preferred radically transferable atom or group xc2x7Hal is xc2x7Cl or xc2x7Br, which is cleaved as a radical from the initiator molecule.
Preferably [In] represents the polymerization initiator fragment of a polymerization initiator of formula (III),
capable of initiating polymerization of monomers or oligomers which polymerization initiator is selected from the group consisting of C1-C8-alkyl halides, C6-C15-aralkylhalides, C2-C8xcex1-haloalkyl esters, arene sulfonyl chlorides, haloalkanenitrites, xcex1-haloacrylates and halolactones, p and q represent one and the other components are as defined above.
The polymerization process in the presence of a compound of formula (III) is known as ATRP (Atom Transfer Radical Polymerization) and WO 96/30421 discloses a controlled or xe2x80x9clivingxe2x80x9d polymerization process of ethylenically unsaturated polymers such as styrene or (meth)acrylates by employing the ATRP method. According to this method initiators are employed which generate a radical atom such as xc2x7Cl, in the presence of a redox system of transition metals of different oxidation states, e.g. Cu(I) and Cu(II), providing xe2x80x9clivingxe2x80x9d or controlled radical polymerization.
Specific initiators are selected from the group consisting of xcex1,xcex1xe2x80x2-dichloro- or xcex1,xcex1xe2x80x2-dibromoxylene, p-toluenesulfonylchloride (PTS), hexakis-(xcex1-chloro- or xcex1-bromomethyl)-benzene, 2-chloro- or 2-bromopropionic acid, 2-chloro- or 2-bromoisobutyric acid, 1-phenethyl chloride or bromide, methyl or ethyl 2-chloro- or 2-bromopropionate, ethyl-2-bromo- or ethyl-2-chloroisobutyrate, chloro- or bromoacetonitrile, 2-chloro- or 2-bromopropionitrile, xcex1-bromo-benzacetonitrile and xcex1-bromo-xcex3-butyrolactone (=2-bromo-dihydro-2(3H)-furanone).
The transition metal in the oxidizable transition metal complex catalyst salt used in the process of the invention is present as an oxidizable complex ion in the lower oxidation state of a redox system. Preferred examples of such redox systems are selected from the group consisting of Group V(B), VI(B), VII(B), VIII, IB and IIB elements, such as Cu+/Cu2+, Cu0/Cu+, Fe0/Fe2+, Fe2+/Fe3+, Ru2+/Ru3+, Ru3+/Ru4+, Os2+/Os3+, Vn+/V(n+1)+, Cr2+/Cr3+, Co+/Co2+, Co2+/Co3+, Ni0/Ni+, Ni+/Ni2+, Ni2+/Ni3+, Mn0/Mn2+, Mn2+/Mn3+, Mn3+/Mn4+, or Zn+/Zn2+.
The ionic charges are counterbalanced by anionic ligands commonly known in complex chemistry of transition metals, such hydride ions (Hxe2x88x92) or anions derived from inorganic or organic acids, examples being halides, e.g. Fxe2x88x92, Clxe2x88x92, Brxe2x88x92 or Ixe2x88x92, fluoro complexes of the type BF4xe2x88x92, PF6xe2x88x92, SbF6xe2x88x92 or AsF6xe2x88x92, anions of oxygen acids, alcoholates or acetylides or anions of cyclopentadiene.
Anions of oxygen acids are, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C1-C8carboxylic acid, such as formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate), unsubstituted or C1-C4alkyl-, C1-C4alkoxy- or halo-, especially fluoro-, chloro- or bromo-substituted phenylsulfonate or benzylsulfonate, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxyphenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate, phosphonates, for example methylphosphonate, ethylphosphonate, propylphosphonate, butylphosphonate, phenylphosphonate, p-methylphenylphosphonate or benzylphosphonate, carboxylates derived from a C1-C8carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, and also C1-C12-alcoholates, such as straight chain or branched C1-C12-alcoholates, e.g. methanolate or ethanolate. Anionic ligands and neutral may also be present up to the preferred coordination number of the complex cation, especially four, five or six. Additional negative charges are counterbalanced by cations, especially monovalent cations such as Na+, K+, NH4+ or (C1-C4 alkyl)4N+.
Suitable neutral ligands are inorganic or organic neutral ligands commonly known in complex chemistry of transition metals. They coordinate to the metal ion through a "sgr"-, xcfx80-, xcexc-, xcex7-type: bonding or any combinations thereof up to the preferred coordination number of the complex cation. Suitable inorganic ligands are selected from the group consisting of aquo (H2O), amino, nitrogen, carbon-monoxide and nitrosyl. Suitable organic ligands are selected from the group consisting of phosphines, e.g. (C6H5)3P, (i-C3H7)3P, (C5H9)3P or (C6H11)3P, di-, tri-, tetra- and hydroxyamines, such as ethylenediamine, ethylenediaminotetraacetate (EDTA), N,N-Dimethyl-Nxe2x80x2,Nxe2x80x2-bis(2-dimethylaminoethyl)-ethylenediamine (Me6TREN), catechol, N,Nxe2x80x2-dimethyl-1,2-benzenediamine, 2-(methylamino)phenol, 3-(methylamino)-2-butanol or N,Nxe2x80x2-bis(1,1-dimethylethyl)-1,2-ethanediamine, N,N,Nxe2x80x2,Nxe2x80x3,Nxe2x80x3-pentamethyldiethyltriamine (PMDETA), C1-C8-glycols or glycerides, e.g. ethylene or propylene glycol or derivatives thereof, e.g. di-, tri- or tetraglyme, and monodentate or bidentate heterocyclic exe2x88x92 donor ligands.
Heterocyclic exe2x88x92 donor ligands are derived, for example, from unsubstituted or substituted heteroarenes from the group consisting of furan, thiophene, pyrrole, pyridine, bis-pyridine, picolylimine, g-pyran, g-thiopyran, phenanthroline, pyrimidine, bis-pyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, bis-thiazole, isoxazole, isothiazole, quinoline, bis-quinoline, isoquinoline, bis-isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene purine, bis-imidazole and bis-oxazole.
The oxidizable transition metal complex catalyst can be formed in a separate preliminary reaction step from its ligands or is preferably formed in-situ from its transition metal salt, e.g. Cu(I)Cl, which is then converted to the complex compound by addition of compounds corresponding to the ligands present in the complex catalyst, e.g. by addition of ethylenediamine, EDTA, Me6TREN or PMDETA.
Preferred is a composition, wherein in the component b3) the oxidizable transition metal in the transition metal complex salt is present as a transition metal complex ion in the lower oxidation state of a redox system.
More preferred is a composition, wherein the transition metal complex ion is a Cu(I) complex ion in the Cu(I)/Cu(II) system.
Another subject of the invention is a process for preparing an oligomer, cooligomer, polymer or copolymer with a polydispersity Mw/Mn between 1 and 3, which process comprises reacting a composition of a) at least one compound of formula (I)
(RG)xe2x80x94Axe2x80x94(Stab)xe2x80x83xe2x80x83(I),
wherein
(Stab) is a light stabilizer radical selected from the group consisting of sterically hindered amines, hydroxyphenyl-s-triazines, hydroxyphenyl-benzotriazols and o-hydroxybenzophenones; A is a spacer group or a direct bond; and
(RG) is a group containing at least one ethylenically unsaturated functional group; with either b1) a compound of formula (II)
Xxe2x80x94Yxe2x80x83xe2x80x83(II),
xe2x80x83wherein
X represents a group having at least one carbon atom and is such that the free radical derived from X is capable of initiating polymerization and
Y represents a group being such that the free radical derived from it forms a stable free radical or b2) a free radical source from which a radical Xxc2x7 is formed capable of initiating polymerization and a stable free radical Yxc2x7; or b3) a compound of formula (III)

xe2x80x83and a catalytically effective amount of an oxidizable transition metal complex catalyst, wherein
p represents a number greater than zero and defines the number of initiator fragments;
q represents a numeral greater than zero;
[In] represents a radically transferable atom or group capable of initiating polymerization and -[Hal] represents a leaving group; and optionally simultaneously or in a subsequent step with c) one or more ethylenically unsaturated monomers or oligomers different from those of formula (I), at a temperature between 50xc2x0 C. and 180xc2x0 C.
Preferably the temperature ranges from about 80xc2x0 C. to about 150xc2x0 C. At temperatures above about 180xc2x0 C., the controlled conversion of the monomers into polymers may decrease, and undesirable by-products like thermally initiated polymers are formed or decomposition of the components may occur.
The isolating step of the present process may be carried out by known procedures, e.g. by precipitation, distilling and filtering off unreacted monomer. After completing the reaction catalyst salts may be filtered off, followed by evaporation of the solvent or by precipitation of polymer in a suitable liquid phase, filtering the precipitated polymer, washing and drying.
The resulting oligomers, polymers, cooligomers and copolymers have a narrow molecular weight distribution. Preferably the polydispersity Mw/Mn is between 1.0 and 2, more preferably between 1.0 and 1.5 and most preferably between 1.0 and 1.4.
Preferred molecular weights Mn are between 1000 and 50 000, more preferred between 1000 and 10 000 and most preferred between 1000 and 5 000.
The process may be carried out in the presence of an organic solvent or in the presence of water or in mixtures of organic solvents and water. Additional cosolvents or surfactants, such as glycols or ammonium salts of fatty acids, may be present. Other suitable cosolvents are described hereinafter.
If organic solvents are used, suitable solvents or mixtures of solvents are typically pure alkanes (hexane, heptane, octane, isooctane), aromatic hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether), esters (ethyl acetate, propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ether), or mixtures thereof.
The aqueous polymerization reactions can be supplemented with a water-miscible or hydrophilic cosolvent to help ensure that the reaction mixture remains a homogeneous single phase throughout the monomer conversion. Any water-soluble or water-miscible cosolvent may be used, as long as the aqueous solvent medium is effective in providing a solvent system which prevents precipitation or phase separation of the reactants or polymer products until after all polymerization reactions have been completed. Exemplary cosolvents useful in the present invention may be selected from the group consisting of aliphatic alcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkyl pyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols, polypropylene glycols, amides, carboxylic acids and salts thereof, esters, organosulfides, sulfoxides, sulfones, alcohol derivatives, hydroxyether derivatives such as butyl carbitol or cellosolve, amino alcohols, ketones, and the like, as well as derivatives thereof and mixtures thereof. Specific examples include methanol, ethanol, propanol, dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol, dipropylene glycol, tetrahydrofuran, and other water-soluble or water-miscible materials, and mixtures thereof. When mixtures of water and water-soluble or water-miscible organic liquids are selected as the aqueous reaction media, the water to cosolvent weight ratio is typically in the range of about 100:0 to about 10:90.
If more than one polymerizable compound of formula (I) is used, copolymers with different light stabilizer structures are formed. These copolymers may be either random or block copolymers. Because the present polymerization is a xe2x80x9clivingxe2x80x9d polymerization, it can be started and stopped practically at will. Furthermore, the polymer product retains the functional alkoxyamine group or the -Hal group allowing a continuation of the polymerization in a living matter. Thus, in one embodiment of this invention, once the first polymerizable compound of formula (I) is consumed in the initial polymerizing step a second polymerizable compound of formula (I) can then be added to form a second block on the growing polymer chain in a second polymerization step. Therefore it is possible to carry out additional polymerizations with the same or different compounds of formula (I) or with other suitable monomers to prepare multi-block copolymers. Furthermore, since this is a radical polymerization, blocks can be prepared in essentially any order. One is not necessarily restricted to preparing block copolymers where the sequential polymerizing steps must flow from the least stabilized polymer intermediate to the most stabilized polymer intermediate, such as is the case in ionic polymerization.
The process is particularly useful for the preparation of block copolymers containing different light stabilizer groups in blocks in the copolymer. A typical example is a block copolymer containing a hydroxy-phenyl-benzotriazol or a hydroxy-phenyl-s-triazine UV-absorber in one block whereas the other block is build from a 2,2,6,6,-tertamethyl-piperidine group.
In addition to the polymerizable compounds of formula (I) conventional monomers can be used as comonomers, which may be desirable in some cases.
Suitable amounts of other comonomers c) are from 1% to 50% by weight based on total monomers.
Suitable ethylenically unsaturated monomers or oligomers have been already given.
The initiator/regulator compound b1) is preferably present in an amount of from 0.1 mol-% to 30 mol-%, more preferably in an amount of from 0.1 mol-% to 20 mol-%, and most preferably in an amount of from 0.5 mol-% to 10 mol-% based on the monomer or monomer mixture.
The majority of compounds of formula (Ia) to (Ij) are known and can be prepared according to standard methods.
Examples wherein the light stabilizer is a hydroxy-phenyl-triazine are given in EP-A-0 434 608, U.S. Pat. No. 5,189,084 or U.S. Pat. No. 5,672,704. Examples wherein the light stabilizer is a hydroxy-phenyl-benzotriazole are given in U.S. Pat. No. 4,785,063 or U.S. Pat. No. 5,112,912. Examples of suitable functionalized benzophenones are given in J. Polym. Sci. (1982), 27(7), 2605-13.
Polymerizable sterically hindered amines (2,2,6,6-tetramethyl-piperidines) are for example disclosed in U.S. Pat. No. 4,210,612, U.S. Pat. No. 4,294,949 or U.S. Pat. No. 4,276,401.
Polymerizable sterically hindered amines from the classes of morpholinone, piperazinone and piperazindione are disclosed in WO 99/14206, GB 2 333 774 and GB 9913511.3.
Definitions and preferences for the different groups and substituents have been given above, they apply also for the process.
The source of radicals in component b2) may be a bis-azo compound, a peroxide or a hydroperoxide.
Preferably, the source of radicals is 2,2xe2x80x2-azobisisobutyronitrile, 2,2xe2x80x2-azobis(2-methylbutyronitrile), 2,2xe2x80x2-azobis(2,4-dimethylvaleronitrile), 2,2xe2x80x2-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1xe2x80x2-azobis(1-cyclohexanecarbonitrile), 2,2xe2x80x2-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl-2,2xe2x80x2-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile, 2,2xe2x80x2-azobis(2,4,4-trimethylpentane), 2,2xe2x80x2-azobis(2-methylpropane), 2,2xe2x80x2-azobis(N,Nxe2x80x2-dimethyleneisobutyramidine), free base or hydrochloride, 2,2xe2x80x2-azobis(2-amidinopropane), free base or hydrochloride, 2,2xe2x80x2-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or 2,2xe2x80x2-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide.
Preferred peroxides and hydroperoxides are acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate, bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butyl permaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate, t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butyl peracetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis (t-butylperoxy) butane, 2,2 bis (t-butylperoxy) propane, dicumyl peroxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy 3-phenylphthalide, di-t-amyl peroxide, xcex1,xcex1xe2x80x2-bis(t-butylperoxy isopropyl)benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl 1,2-dioxolane, di-t-butyl peroxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide, 3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-xcex1-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.
These compounds are commercially available.
If more than one radical source is used, a mixture of substitution patterns is obtainable.
If b2) a free radical source and a stable free radical are applied separately, the stable free radical is preferably present in an amount of from 0.1 mol-% to 30 mol-%, more preferably in an amount of from 0.1 mol-% to 20 mol-%, and most preferably in an amount of from 0.5 mol-% to 10 mol-% based on the monomer or monomer mixture.
The molar ratio of the radical source to the stable nitroxyl radical may be from 1:10 to 10:1, preferably from 1:5 to 5:1 and more preferably from 1:2 to 2:1.
If b3) is applied, the compound of formula (III)
is preferably present in an amount of from 0.1 mol-% to 30 mol-%, more preferably in an amount of from 0.1 mol-% to 20 mol-%, and most preferably in an amount of from 0.5 mol-% to 10 mol-% based on the monomer or monomer mixture.
A catalytically effective amount of an oxidizable transition metal complex catalyst is preferably 100 ppm to 1%, more preferably 100 ppm to 5000 ppm based on the monomer or monomer mixture. Preferably the molar ratio of complexing agent to transition metal is from 1:5 to 5:1, more preferably from 2:1 to 1:2.
If the process b3) is applied the resulting polymer oligomer contains at its end a halogen atom. This halogen atom can be exchanged by reacting a stable free radical Yxc2x7 with the oligomer or polymer. In this case the free radical is attached to the polymer and the halogen atom is removed. The exchange process is described in PCT/EP 99/06924.
Another subject of the invention is a oligomer, polymer, cooligomer copolymer obtainable by the above mentioned processes.
Still another subject of the invention are the compounds 1,1,3,3-Tetraethyl-2-(1-phenyl-ethoxy)-2,3-dihydro-1.H.-isoindole, 1-(1,1,3,3-Tetraethyl-1,3-dihydro-isoindol-2-yloxy)-cyclohexanecarbonitrile or N-(1,1,3,3-tetramethyl-butyl)-N,O-bis-(1-cyano-1-methyl-ethyl)-hydroxylamin. These compounds used as polymerization regulators PR3, PR4 and PR5 are new.
The oligomers, polymers cooligomers or copolymers obtained by the present process are useful as light or heat stabilizers, particular UV-light stabilizers of organic materials. Preferred organic materials are natural or synthetic polymers. Examples are given below.
The term heat or light stabilizer in the context of the present invention means stabilization against the influences of heat and/or actinic or electromagnetic radiation ranging from xcex3 to infrared.
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density arid high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins; i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerization (normally under high pressure and at elevated temperature).
b) b catalytic polymerization using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either xcfx80- or "sgr"-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or, IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density. polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(xcex1-methylstyrene).
6. Copolymers of styrene or xcex1-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.
7. Graft copolymers of styrene or xcex1-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from xcex1,xcex2-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl-halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplazstic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
Still a further subject of the present invention is the use of a oligomer, polymer, cooligomer, or copolymer of formula (III), (IIIa); (IIIb), (IIIc), (IIId), (IIIe) or (IIIf) as light stabilizers for organic materials, particularly for natural and synthetic polymers.
Most preferred are thermoplastic polymers and crosslinked polymers, such as thermosetting enamels, paints, laquers and varnishes.
Also subject of the present invention are organic materials stabilized against UV-light with a oligomer, polymer, cooligomer or copolymer of formula (III), (IIIa), (IIIb), (IIIc), (IIId), (IIIe) or (IIIf).

Polymeric stabilizers having low polydispersity

Abstract: wherein

Abstract: Y represents a group being such that the free radical Yxc2x7 derived from it forms a stable free radical; or b2) a stable free radical Yxc2x7 and a free radical source from which a radical is formed capable of initiating polymerization, or b3) a compound of formula (III)

Abstract: [In] represents a radically transferable atom or group capable of initiating polymerization and -[Hal] represents a leaving group; and optionally c) one or more ethylenically unsaturated monomers or oligomers different from those of formula (I). Further subjects of the invention are a polymerization process, the polymers, copolymers oligomers and cooligomers obtainable by this process and the use of the polymers, copolymers oligomers and cooligomers as heat or light stabilizers.


A transfer sheet has a base layer and a specific surface layer. In a plot graph with load P (mN) as ordinate and the square of indentation depth A (xcexcm) as abscissa, plotted when the tip of a diamond triangular pyramid penetrator having a dihedral angle of 80xc2x0 is pressed in on the side of the surface layer, the plot graph has a first flexing point that appears first, a first region extending from the first flexing point to zero and a second-and-further region subsequent to the first flexing point, and a gradient H of the graph in the first region is 0.09 mN/xcexcm2 or smaller. Also disclosed are image-forming methods making use of such a transfer sheet. The transfer sheet has a superior effect of keeping dot toner images from scattering at the time of transfer. The base layer is paper made from pulp.

1. Field of the Invention
This invention relates to a transfer sheet. More particularly, it relates to a transfer sheet which is a transfer material to which, in electrophotographic apparatus or electrostatic printers, a toner image obtained by forming an electrostatic latent image on an image-bearing member such as a photosensitive member and developing the electrostatic latent image is transferred, and an image-forming method making use of such a transfer sheet.
2. Related Background Art
In electrophotographic apparatus, after an electrostatic latent image has been formed on a photosensitive member, the toner of a developer is made to adhere electrostatically to the electrostatic latent image to form a toner image, and this toner image is transferred to a transfer sheet (paper) by means of a transfer assembly. As transfer assemblies of this type, electrostatic transfer means such as corona transfer means and roller transfer means are known in the art.
The progress of electrophotography has taken place in copying machines. With the spread of its application to output machinery, such as page printers and facsimile machines, it has made an advance from analog systems to digital systems and is increasingly demanded to achieve higher function, more coloration and higher image quality.
Nowadays, in most electrophotographic apparatuses, the toner image held on the photosensitive member is transferred to plain paper by an electrostatic transfer means as mentioned above, where images may greatly deteriorate at the time of transfer. This deterioration causes inferior images formed by printing and ink-jet recording.
Recently, in the field of ink-jet recording other than electrophotography, it was really shocking that replacement of sheets with special exclusive sheets has brought about a dramatic improvement in image quality.
In respect of sheets of transfer sheets for electrophotography, too, a variety of proposals have been made in order to improve transfer performance and image quality. In particular, properties having energetically been studied include electrical properties, such as volume resistivity and surface resistivity of sheets. For example, in Japanese Patent Publications No. 41-20152 and No. 43-4151, it has been proposed to maintain volume resistivity within a stated range; in Japanese Patent Application Laid-Open No. 50-117435, it has been taught to provide a resin layer having a volume resistivity of 3xc3x971013 xcexa9xc2x7cm or above on the surface of transfer paper; and it has been taught in Japanese Patent Application Laid-open No. 56-16143, to provide on a transfer paper""s base layer firstly a low-resistance layer and then at the outermost surface a high-resistance layer to make up a transfer sheet. In an actual service environment, however, it has been so difficult to control moisture in the air and that it has been unable to stabilize electrical resistance of transfer sheets. Accordingly, as disclosed in Japanese Patent Application Laid-open No. 5-53363, it is proposed to incorporate in a sheet a synthetic hectorite having a specific crystal structure, attempting to make a resistance value environmentally stable. Even this proposal, however, cannot provide images on the level comparable to the level of those formed by ink-jet recording or by printing.
As an approach from a different aspect, there has been a method in which an elastomer is coated on the surface of transfer paper, as disclosed in Japanese Patent Application Laid-open No. 49-126334. In an attempt to make image evaluation on a color electrophotographic apparatus by actually coating on transfer paper the material disclosed therein, no remarkable effect was observable with regard to the reproduction of a photographic image on a 400 dpi digital printer.
As the cause of image deterioration in the transfer process as stated above, it can be concluded that, a dithered pattern formed as a result of image processing employed by recent printers or a toner image formed of continuous minute individual dots by PWM (pulse width modulation) stands scattered when digital data are outputted. This tends more remarkably in the case of, e.g., very fine dots of a screen on which small characters or image data are formed. A one-dot toner image that constitutes binary image data of 400 dpi has a size of about 64 xcexcm. As for the improvement in dot reproducibility of about such size, it cannot be expected at all by any conventional means stated above, showing capability not different at all from ordinary transfer sheets. More specifically, in conventional means, ink-jet recording enables reproduction of 800 dpi photographic images, whereas electrophotographic processing has been unsatisfactory in any effort to reproduce true 400 dpi photographic images, because of the image deterioration (a decrease in gradation) caused in the transfer process.
However, even though the means disclosed in the above Japanese Patent Application Laid-open No. 49-126334 is old, the inventors have been interested in that its means relies on a mechanical phenomenon which may hardly be affected by environmental factors, different from other resistance values or the like. However, has been found that, even for soft elastomers used at present in, e.g., intermediate transfer members of the latest color copying machines, it is difficult to transfer binary images (toner images) of 400 dpi without scattering.
Japanese Patent Application Laid-open No. 9-170190 discloses a transfer sheet made to have a fibrous surface as a recording sheet for output machinery of various types. This publication discloses that its fibers exhibit a cushioning performance and hence can make dry-process electrophotographic toner images sharp. However, as also shown in its Examples, the thickness of the fiber used, though fairly as small as 0.5 denier, is only on the level of the particle size of electrophotographic toners. Hence, the cushioning performance exhibited by fibers which mutually slide as so described in the above publication may be expectable for making large-size characters or the like sharp at best, but is not so expectable as to absorb kinetic energy of individual toner particles as aimed in the present invention. Materials disclosed as examples in the above publication are celluloses and polyester resins, which are materials of the same nature as, or harder than, those of toners, and hence, as the materials alone, they are not expectable at all for any cushioning performance on individual toner particles.
An object of the present invention is to provide a transfer sheet having solved the above-noted problems, and an image-forming method making use of the transfer sheet.
More specifically, an object of the present invention is to provide an electrophotographic transfer sheet which has a superior effect of keeping dot toner images from scattering at the time of transfer, and an image-forming method making use of the transfer sheet.
To achieve the above-noted object, the present invention provides a transfer sheet comprising a base layer and a surface layer formed on at least one surface of the base layer, wherein;
in a plot graph with load P (mN) as ordinate and the square of indentation depth A (xcexcm) as abscissa, plotted when the tip of a diamond triangular pyramid penetrator having a dihedral angle of 80xc2x0 is pressed in on the side of the surface layer;
the plot graph has a first flexing point that appears first, a first region extending from the first flexing point to zero and a second-and-further region subsequent to the first flexing point; and
a gradient H of the graph in the first region is 0.09 mN/xcexcm2 or smaller; and
the base layer includes paper made from pulp.
The present invention also provides an image-forming method comprising;
a toner image forming step of forming a toner image by means of a toner; and
a transfer step of transferring the toner image formed, to a transfer sheet;
wherein;
the transfer sheet has a base layer and a surface layer formed on at least one surface of the base layer; and
in a plot graph with load P (mN) as ordinate and the square of indentation depth A (xcexcm) as abscissa, plotted when the tip of a diamond triangular pyramid penetrator having a dihedral angle of 80xc2x0 is pressed in on the side of the surface layer;
the plot graph has a first flexing point that appears first, a first region extending from the first flexing point to zero and a second-and-further region subsequent to the first flexing point; and
a gradient H of the graph in the first region is 0.09 mN/xcexcm2 or smaller. and
the base layer includes paper made from pulp.


A system and method for automatically changing channels. A user selection of a channel and a time associated with media content is received. The current time is determined. A display is powered on in response to determining the display is off. A display is automatically changed to the channel in response to the current time matching the selected time. The media content received through the channel is displayed.

The use of and development of entertainment technologies has grown nearly exponentially in recent years. The growth is fueled by larger communications networks with more reliable protocols and smart devices enabled with cutting edge hardware and software. For example, the distribution of media content through satellite, cable, Internet Protocol television (IPTV), and other communications connections has vastly increased the media options to one or more users.
Despite the improvements in media related technologies, the selection of television programming, video-on-demand (VOD), or other media content has not changed significantly. Typically a user utilizes an electronic or hard copy of a programming guide or schedule to manually change a channel or otherwise select to display media content. The selection is usually made at the time the user watches the content if the user is able to remember the relevant information, such as channel and time.

System and method for an automatic television channel change


A crane comprises a lower frame having an upper frame rotatably mounted thereon. A pair of rear roadwheels are rotatably mounted on either end of an axle housing pivotally mounted on the lower frame and suspended thereunder by a pair of laterally spaced suspension cylinders. A boom, pivotally mounted on the upper frame, is adapted to be lowered and positioned forwardly of the crane when it is driven to a remote job site. During such forward positioning of the boom, either when loaded or unloaded, a cam secured to the upper frame trips an air valve for opening a pair of slave valves to communicate hydraulic fluid between the head ends of the suspension cylinders to permit the axle to oscillate. When the crane is placed in operation and the upper frame is rotated on the lower frame, the cam will release the air valve which closes the slave valves to block communication of hydraulic fluid between the suspension cylinders whereby the axle is placed in a lock-out condition of operation. The rod ends of the suspension cylinders are preferably disposed in unattached relationship adjacent to the axle housing, but could be secured thereto.

Construction vehicles, such as cranes, excavators and the like, normally comprise an upper frame rotatably mounted on a lower frame and a boom pivotally mounted on the upper frame. Either the front or rear pairs of roadwheels are normally supported under the lower frame by a pair of laterally spaced suspension cylinders pivotally interconnected between an axle housing for each pair of roadwheels and the lower frame. When the vehicle is driven to a remote job site, it is desirable to place the suspension cylinders in a "roading" condition of operation whereby hydraulic fluid may be communicated therebetween to permit the axle housing to oscillate about a pivot means pivotally mounting the axle housing on the lower frame.
Upon the arrival at such job site and during performance of work thereat, it is further desirable to lock-out the performance of work thereat, it is further desirable to lock-out the suspension cylinders to stabilize the vehicle, except when the boom is positioned straight-forward. Conventional lock-out systems of this type normally comprise a separate control valve or in some cases a fluid circuit responsive to activation of the drive motor for the roadwheels which functions to release the cylinders from the lock-out condition of operation and thus place them in the "roading" condition of operation whereby the axle housing is permitted to oscillate for smooth driving purposes. Since the rod end of each suspension cylinder is pivotally connected to the axle housing, an operator cannot detect whether or not the suspension cylinders have been placed in such a "roading" condition of operation.

Lock out means for pivotal axle suspension cylinders


A method for managing an interruption of emission, in an aircraft, of an acoustic message including an information item about a state of part of the said aircraft and/or about its environment, wherein the acoustic message is structured into one or more successive acoustic fragments each representative of the information item, the method includes the steps of: delaying, starting from a given moment, the execution of a decision to interrupt the emission of the acoustic message until the end of emission of an acoustic fragment that is in the course of emission at the given moment; and executing the interruption decision.

The present invention relates to a method and an associated system for managing an interruption of the emission of an acoustic message in an aircraft.
In an aircraft cockpit, different monitoring systems are in charge of emitting alert messages in case of detection of an abnormal situation.
Firstly, the flight alert system ("Flight Warning System" for FWS for flight alert system, "Flight Warning Computer" for flight alert computer or else "Flight Warning Application" for flight alert application) is an on-board system intended to forewarn the crew members of an abnormal situation concerning a monitored system of the airplane.
The monitored systems may include detectors or calculators relating, for example, to the engines, to the fuel tanks or to the landing gears.
The flight alert system also emits automatic altitude announcements when the airplane passes through certain altitudes.
Furthermore, other monitoring systems have the function of forewarning the crew of risks related to the environment of the aircraft.
This is the case of the systems known as TAWS ("Terrain Awareness and Warning System" or impact warning and alert system), GPWS ("Ground Proximity Warning System" or ground proximity warning device), TCAS ("Traffic Collision Avoidance System" or on-board anti-collision system, also known as ACAS), WxR ("Weather Radio" or weather radar) or PWS ("Predictive Windshear System", a shear prediction system).
It is possible to integrate several of the equipment items that monitor the environment of the aircraft in a single monitoring system, known, for example, as AESS ("Aircraft Environment Surveillance System" or aircraft environment monitoring system).
These different alert systems, whether their function is to monitor a system of the aircraft or of its environment, communicate with the pilot by alert messages, which may include texts on screens, the illumination of lamps and/or acoustic messages, which may include voice syntheses.
The solution adopted until now to manage alert messages involved preliminary classification of alert conditions into two categories: high-priority alert conditions and normal-priority alert conditions.
In the event of detection of a normal-priority alert condition by an alert system, the corresponding acoustic message is activated immediately, except if an acoustic message associated with a high-priority alert condition is in the course of emission.
When a normal-priority alert condition is detected while a high-priority acoustic message is in the course of emission, the acoustic message in the course of emission is continued until the end of detection of the corresponding alert condition or until the end of emission of the acoustic signal, in the case of a signal that can be stopped before the end of detection of the corresponding alert condition. The normal-priority acoustic message is then emitted if the associated alert condition is still in existence at that moment.
In the case of detection of a high-priority alert condition by an alert system, the corresponding acoustic message is activated immediately.
If a normal-priority acoustic message is already in the course of emission, the acoustic message in the course of emission is interrupted immediately and the new acoustic message is emitted.
This method has the disadvantage that it does not take into account the content of the message in the course of emission, and therefore it risks interrupting emission of this message without taking into account the intelligibility of this content by the pilot.
Document TSO-C151a ("Technical Standard Order") presents such a solution of the type used heretofore.

Process and system for managing an interruption of a broadcast of a sonorous message in an aircraft


An alloy includes lithium, silicon and tin. An anode may be formed of an anode material containing the alloy of lithium, silicon and tin. The anode material may include an electrolyte. The anode material may be a pressed powder pellet that is solid at ambient temperature. A battery, for example, a thermal battery, can contain an electrolyte-separator, a cathode, and/or an anode with the alloy of lithium, tin and silicon. The anode formed of the alloy consisting of lithium, tin and silicon can have a melting point from about 500° C. to about 600° C. or higher making it suitable for use in a thermal battery.

The field of this disclosure generally relates to alloys capable of use as an anode material in batteries. The disclosure also relates to a composite material capable of use as an anode material that contains the alloy, and to batteries (e.g., thermal batteries) that contain such anode materials.
Thermal batteries tend to have relatively long shelf lives, high energy densities, require relatively low maintenance, and can withstand relatively high temperatures. Thermal batteries also tend to provide a short burst of power over a relatively short period of time. The burst may range from less than a second to an hour or more, with power typically ranging from about a watt or less to kilowatts. Such properties make thermal batteries suitable for military (e.g., batteries for missile guidance systems) and space exploration applications. Thermal batteries also are useful as back-up batteries in applications that require high reliability. Thermal batteries may also be used in other applications, such as in electric vehicles.
A typical thermal battery includes an anode, a cathode, an electrolyte-separator containing a solid electrolyte that is non-conductive at ambient temperature, and a pyrotechnic material (e.g., heat pellet, which may contain, for example, Fe—KClO4 powder) that provides a heat source to the battery. When battery operation is desired, an external stimulus is applied to the battery. For example, an electrical current may be applied to the battery to set off an electric match or an electro-active squib, or a mechanical force (e.g., mechanical shock) may be applied to set off a concussion primer. The external stimulus causes the pyrotechnic material to ignite and begin to heat. Heat produced from the pyrotechnic material causes the previously solid electrolyte to melt and become conductive, which allows the battery to provide power for a desired application.
Thermal batteries are often formed using pellet techniques, such that each of the electrolyte, cathode, anode, and heat source are formed into a wafer (pellet). In this case, the respective cell component chemicals are processed into powders and the powders are pressed together to form the wafer (or pellet). Each component may be formed as a discrete part, or the anode and/or cathode may include (i.e., be flooded with) electrolyte material to improve the conductivity of that component. The electrolyte material in the anode and cathode may or may not contain binder material.
Electrolytes for use with thermal batteries often include a eutectic mixture (i.e., a mixture which melts at a temperature lower than each of the individual components) of lithium chloride and potassium chloride and a binder (such as MgO, fumed silica or kaolin), which assists in containing the electrolyte within the thermal battery assembly upon melting, such as by capillary action, surface tension, or both. With typical thermal battery electrolyte-separators, a binder prevents the electrolyte material from dispersing throughout the battery, which would cause undesired shunts or short circuits in the cell.
Cathode materials for thermal batteries may vary in accordance with a variety of design parameters and generally include a metal oxide or metal sulfide. By way of example, iron oxide (Fe3O4), iron disulfide (FeS2) or cobalt disulfide (CoS2) are often used as cathode materials.
The anodes of thermal batteries are generally formed of an alkali or alkaline earth metal or alloy. A typical anode includes lithium metal or a lithium alloy, such as lithium aluminum, lithium silicon, or lithium boron.
A thermal battery may consist of a single series of stacked cells or two or more parallel stacks of the series of stacked cells. The cell stack(s) may be insulated as thoroughly as possible, placed in a container, which may be made of stainless steel, and the container is sealed to form a hermetic seal, such as by welding. Electrical connections may be provided through standard glass to metal seals.
As noted above, typical thermal batteries make use of lithium-aluminum and lithium-silicon anode alloys. In order to reduce the volume of the anode pellets, the density of the anode pellets is increased by adding iron powder to the lithium-aluminum or lithium-silicon alloy powder prior to pressing. However, the iron does not contribute to the performance of the anode.
A continuing need exists for anode materials that are formed of alloys that result in improvements in conductivity, voltage, impedance, and lifetime without sacrificing density and volume. A continuing need also exists for primary batteries, such as thermal batteries, that incorporate such materials and exhibit such improved performance.

Li—Si—Sn alloy, anode material of the alloy, and batteries including same


A digital receiver to effect display of at least one of video or a plurality of background information blocks each indicative of a program time period, including: a display change controller provided in the digital receiver, which changes a displayed shape of a particular background information block indicative of a program time period in the grid when the program time period indicated by the particular background information block exceeds a program time period which is displayed in a first prescribed zone; a full display controller controlling display of the program start time and program end time to occur concurrently together with the selected background information block on a same display whenever the selected background information block is selected.

The present invention relates to a broadcasting and communication receiver apparatus which receives information about a transmission program together with video and audio data, decodes and displays the program-associated data and more particularly, to a receiver apparatus which can display program-associated information.
In a prior art television signal receiver apparatus, program information such as the title, start and end times of a broadcasting program has not been transmitted together with video and/or audio signal and thus it has been impossible to display these information on a television display screen. For this reason, TV viewers have acquired these information from a program schedule chart run in newspaper.
Further, digital broadcasting has been being started in which digitized signals in place of conventional analog TV signals are transmitted to each home via satellite, cable or land-based broadcasting. Satellite broadcasting has been already realized in such a manner and, even in Japan, plans have been already in the works for start of such service. In the digital broadcasting, various sorts of additional information can be transmitted simultaneously with digitized video and audio signals. When such additional information can be used to prepare a program schedule chart.
Meanwhile, even in the conventional analog broadcasting, when such a system is employed that program-associated information is multiplexed during vertical blanking interval, a program chart similar to that in the digital broadcasting case can be prepared.
FIG. 1 is a block diagram of a multiplex system of an analog broadcasting type, in which SA denotes an audio signal, SV a video signal, SP program-associated information such as a title, start and end times of a broadcasting program. Reference number 1 denotes a multiplexer for multiplexing the video signal SV and the program-associated information SP, numeral 2 denotes a modulator for modulating the video signal SV and the audio signal SA into broadcasting electromagnetic wave.
In the analog broadcasting system, there is employed a method for multiplexing the program-associated information SP during the vertical blanking interval. However, the amount of information capable of multiplexing during the vertical blanking interval is small when compared with the amount of information transmittable in the digital broadcasting system. In the analog broadcasting system, further, with respect to its screen displaying function, its screen displaying ability as well as the amount of information to be handled are restricted. Therefore, the display screen implemented based on the analog broadcasting system is inferior in presentation ability to that based on the digital broadcasting system.
FIG. 2 is a block diagram of a multiplex system of a digital broadcasting type, in which reference symbols 3A, 3B and 3P denote encoders for encoding the audio and video signals and program-associated information respectively. In the digital broadcasting system, the audio signal SA, video signal SV and program-associated information SP are encoded and compressed respectively by the encoders 3A, 3B and 3P, and then subjected by the multiplexer 1 to a time division multiplexing operation to obtain a multiplexed signal. The multiplexed signal is modulated by the modulator 2 into broadcasting electromagnetic wave.
The digital broadcasting system is featured in that, since the program-associated information SP is encoded and compressed by the encoder 3P, more signals can be multiplexed than the program-associated information multiplexable in the analog broadcasting system.
When it is desired to display such program-associated information as program chart on a predetermined display zone of a display screen, e.g., a television display screen, if a display zone necessary for full display of all the display data is larger than the predetermined display zone, then all the display data cannot be fully displayed on the limited display zone. For this reason, there disadvantageously occurs such a situation that part of the originally-displayable information is missing.

This patent is subject to a terminal disclaimer.

Broadcasting and communication receiver apparatus


Methods, systems, and computer program products used to locate a feature in an image, including identifying one or more candidate features in an image, where each candidate feature is a group of pixels in the image that satisfies a pattern-matching criterion. A best candidate feature is selected from the one or more candidate features, and a parameterized shape is fit to the image in the region of the best candidate feature to compute a feature shape corresponding to the best candidate feature. Particular implentations can include one or more of the following features. The candidate feature is a candidate pupil and the feature shape is an ellipse. Fitting the parameterizes shape to the mage includes applying an iterative process varying shape parameters. The parameterized shape encloses pixels in the image, and fitting the parameterized shape to compute an inner value, summing functions of values of pixels in the image outside of the parameterized shape to compute an outer value, and maximizing a difference between the inner value and the outer value.

The present invention relates to digital image processing.
Locating pupils in a digital image is useful in some situations. For example, flash photographs of people frequently result in a red-eye effect that can be corrected if the location of the pupil is known. The red-eye effect is a consequence of the flash illumination reflecting off of the subject's retina, returning to the camera, and appearing as a bright red dot where the pupil should be. Similar effects occur with photographs of animals, although the dot color can be different (e.g., green or yellow). Computer applications for editing images typically include tools to assist a user in correcting the red-eye effect—usually by replacing the red pupil with a more natural-looking pupil. In order to avoid requiring the user to designate precisely which pixels constitute the pupil to be corrected, such a tool can include a detector that determines the pupil position and shape to within some margin of error. In order to be sufficiently reliable, such a detector typically requires (through user action) a rough initial hint of the pupil location and size.


A high frequency amplifying system includes an input coupling circuit having an input terminal for receiving a high frequency signal, a pair of amplifiers, and an impedance mismatch circuit for coupling each amplifier to a respective output terminal of the coupling circuit. The impedance mismatch circuit is controllable by a control signal supplied thereto to produce a selected degree of mismatch between the coupling circuit and the input impedances of the amplifiers, to thereby provide adjustable gain control of the amplifying system. The coupling circuit introduces phase shifts between the input and output terminals thereof which attenuates reflection therebetween of intermodulation products resulting from the presence of interfering signals at any of such terminals.

1. Field of the Invention
The present invention concerns a high-frequency amplifier arrangement comprising an input coupling circuit which has at least a first and a second access to couple a first and a second system, at least one of which is an amplifier.
Such amplifier arrangements according to the invention are particularly used for base transceiver stations of a mobile radio network. Such a network is, in effect, formed by various base transceiver stations covering each a defined geographical area and transmitting over various frequency channels which are very close together. In order to avoid interference among areas, the output power of each base transceiver station is to be strictly limited to the coverage area.
2. Description of the Related Art
A high-frequency amplifier is specifically known from French Patent Specification no. 1452462. However, no output power controller is provided.
For making the output power of the amplifiers vary, PIN-diode attenuators are known to be used. However, when the diodes used in such attenuators are to be capable of carrying high power levels, higher than 10 mW for example, they become very costly.

High-frequency amplifier arrangement, transceiver station comprising such an amplifier arrangement and mobile radio system comprising such stations


A curved blade overlays the marginal portion of a photocopier drum photosensitive surface at the transfer station to engage copy sheets and direct them to a transport assembly removing the sheets from the transfer station. The blade is pivotally mounted at one end and connected to a reciprocating actuator at the other end. It is pivoted away from its overlaying position, after the transport assembly engages the leading corner of the sheet so that the sheet can then contact the marginal portion, and back to its overlaying position after the trailing edge of the sheet has left the surface of the drum. In one embodiment the actuator is mechanically responsive to the photocopier scanner. In another embodiment, the blade is pivotable about an intermediate portion, and the actuator is operated by a solenoid energizable by a switch at the appropriate times.

The invention relates generally to photocopiers employing liquid toner developer and particularly to apparatus for stripping sheets from a photosensitive drum after transfer of the developed image from the drum to the sheet.
In a photocopier employing a rotating photosensitive drum surface, the drum surface is first electrically charged. It is then exposed to a light pattern generated by a scanner passing over an original and focused on the drum, to form a latent electrostatic image on the drum surface. The latent image is developed, and the developed image is transferred to a sheet of transfer material brought into contact with the surface image. The sheet is then transported away from the surface toward an exit tray. It becomes the desired copy of the original.
The sheet brought into contact with the surface of the drum ordinarily adheres closely to it, because of the electrostatic fields created during the photocopying process and, in the case of liquid toner copiers, because of the surface tension created by the liquid toner. The sheet must be stripped off the drum, and various methods have been developed to perform this function with a minimum of disturbance to the other elements of the copying system. One method is to blow a stream of air between the copy sheet and the surface of the drum to lift the leading edge of the copy sheet so that it may be gripped and conveyed from the drum. This method has the disadvantage of potentially disturbing the toner particles adhering to the copy sheet. In another method known to the art the sheet stripping is accomplished by claws brought into engagement with the drum. This method has the disadvantage of requiring the claws to be in contact with the drum surface, so the drum surface may become worn or damaged.
Another method, described more fully in U.S. Pat. No. 3,936,045, provides for stripping members in strip or string form in which the strip or string is pressed against an edge of the drum photosensitive surface. When the copy sheet is brought to the drum, an edge of the copy sheet slides along the member. The member includes a forward portion increasingly spaced away from the drum surface to guide a portion of the leading edge of the copy sheet to engagement by a strip-off device. A disadvantage of this approach is that an entire edge of the copy sheet is kept from contact with the drum surface and is therefore unavailable for copying. The pressure of the member against the drum photosensitive surface also may wear or damage the surface.
It is a principal object of this invention to provide a sheet stripping apparatus that minimizes interference with the photocopying process and reduces potential damage and wear to portions of the photosensitive surface. It is another important object of the invention to provide a sheet stripping apparatus that maximizes the amount of transfer sheet surface available for copying. A further object of the invention is to provide a sheet stripping apparatus that is reliable, durable, and substantially maintainance free.