There are disclosed a polybutadiene composition comprising:

The present invention relates to polybutadiene compositions.
Polybutadiene polymers having butadiene units as their polymerization unit have been widely used for the production of various molded articles, since they exhibit same strength and elastic property as vulcanized elastomers. However, polybutadiene polymers are apt to form gelled product by heat-melting, which led to bad appearance of molded articles produced therefrom.
According to the present invention, formation of gelled products is efficiently prevented and the composition of the present invention is suitably used for the production of molded articles.
The present invention provides:
a polybutadiene composition comprising:
(a) (a-1) a polybutadiene type polymer, and
(a-2) at least one compound selected from
a compound of formula (I-1):
or a compound of formula (I-2):
wherein R11, R12, R13, R14, R15, R16, R17, R18, R21, R22, R23, R24, R25, R26, R27, and R28 are the same or different and independently represent a hydrogen atom, an alkyl group, an alkoxy group, a benzyloxy group, a hydroxy group, a carboxyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, or a benzyloxycarbonyl group; or
(b) (b-1) a polybutadiene type polymer, and
(b-2) a compound of formula (II):
wherein R1, R2 and R4 independently represent a hydrogen atom, or an alkyl group,
R3 represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or an acetyl group,
R5, R6, R7 and R8 independently represent a hydrogen atom, an alkyl group, or a phenyl group which may be substituted with an alkyl group, and
R9 and R10 independently represent a hydrogen atom, an alkyl group, or an alkenyl group; or
(c) (c-1) a styrene-butadiene copolymer, and
(c-2) a benzoin compound;
an article molded from the composition as described above, and processes for producing the composition and the article.
A description will be made to a first aspect of the polybutadiene composition, which comprises
(a-1) a polybutadiene type polymer, and
(a-2) at least one compound selected from a compound of formula (I-1) or a compound of formula (I-2).
The polybutadiene polymer that may be used in the present invention means a polybutadiene polymer comprising butadiene, as a monomer unit, or a copolymer comprising butadiene and another monomer.
Examples of the polybutadiene type polymer described above include, for example, polybutadiene, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene block copolymers and high-impact polystyrenes. These butadiene polymers can be produced by a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method or the like. The polybutadiene polymer may be either a resin or a rubber.
The polybutadiene may be a polybutadiene rubber produced by a solution polymerization method or an emulsion polymerization method.
Preferred polybutadiene type polymer in (a) is polybutadiene polymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, or styrene-butadiene block copolymer.
More preferred polybutadiene type polymer in (a) is styrene-butadiene block copolymer.
R11, R12, R13, R14, R15, R16, R17, R18, R21, R22, R22, R23, R24, R25, R26, R27, and R28 groups in the compounds of formula (I-1) and formula (I-2) will be explained below.
Examples of the alkyl group include, for example, an alkyl group having about 1 to 6 carbon atoms.
Specific examples thereof include, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 2-ethylbutyl group, a n-pentyl group, a 1-methylpentyl group, a 1,3-dimethylbutyl group, a n-hexyl group, a cyclopentyl group, a cyclohexyl group and the like.
Examples of the alkoxy group include, for example, an alkoxy group having about 1 to 6 carbon atoms.
Specific examples thereof include, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxuy group, a t-butoxy group, a 2-ethylbutoxy group, a n-pentyloxy group, a 1-methylpentyloxy group, a 1,3-dimethylbutyloxy group, a n-hexyloxy group, a cyclopentyloxy group, a cyclohexyloxy group and the like.
Examples of the acyl group include, for example, an alkanoyl group having about 1 to 6 carbon atoms, a benzoyl group and the like.
Specific examples thereof include, for example, an acetyl group, a propoinyl group, an isopropionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovarelyl group, a pivaroyl group, a hexanoyl group, a cyclopentylcarbonyl group and the like.
Examples of the acyloxy group include, for example, an acyloxy group having about 1 to 6 carbon atoms.
Specific examples thereof include, for example, an acetyloxy group, a propoinyloxy group, an isopropionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovarelyloxy group, a pivaroyloxy group, a hexanoyloxy group, a cyclopentylcarbonyloxy group and the like.
Examples of the alkoxycarbonyl group include, for example, an alkoxycarbonyl group having about 1 to 6 carbon atoms. Specific examples thereof include, for example,
a methoxycarbonyl group, an ethoxycarbonyl group,
a n-propoxycarbonyl group, an isopropoxycarbonyl group,
a n-butoxycarbonyl group, an isobutoxycarbonyl group,
a sec-butoxuycarbonyl group, a t-butoxycarbonyl group,
a n-pentyloxycarbonyl group, a cyclopentyloxycarbonyl group, and the like.
Preferred compounds of formula (I-1) are a compound of formula (I-1), wherein R15, R16, R17 and R18 are a hydrogen atom.
Specific examples of the compound of formula (I-1) include, for example, 2-chromanone, 3,4-dihydrocoumarine, 5-methyl-3,4-dihydrocoumarine, 6-methyl-3,4-dihydrocoumarine, 7-methyl-3,4-dihydrocoumarine, 8-methyl-3,4-dihydrocoumarine, 5-ethyl-3,4-dihydrocoumarine, 6-ethyl-3,4-dihydrocoumarine, 7-ethyl-3,4-dihydrocoumarine, 8-ethyl-3,4-dihydrocoumarine, 5,6-dimethyl-3,4-dihydrocoumarine, 5,7-dimethyl-3,4-dihydrocoumarine, 5,8-dimethyl-3,4-dihydrocoumarine, 6,7-dimethyl-3,4-dihydrocoumarine, 6,8-dimethyl-3,4-dihydrocoumarine, 7,8-dimethyl-3,4-dihydrocoumarine, 5-methyl-6-ethyl-3,4-dihydrocoumarine, 5-methyl-7-ethyl-3,4-dihydrocoumarine, 5-methyl-8-ethyl-3,4-dihydrocoumarine, 6-methyl-7-ethyl-3,4-dihydrocoumarine, 6-methyl-8-ethyl-3,4-dihydrocoumarine, 7-methyl-8-ethyl-3,4-dihydrocoumarine, 5-ethyl-6-methyl-3,4-dihydrocoumarine, 5-ethyl-7-methyl-3,4-dihydrocoumarine, 5-ethyl-8-methyl-3,4-dihydrocoumarine, 6-ethyl-7-methyl-3,4-dihydrocoumarine, 6-ethyl-8-methyl-3,4-dihydrocoumarine, 7-ethyl-8-methyl-3,4-dihydrocoumarine, and the like.
Specific examples of the compound of formula (I-2) include, for example, 4-chromanone, 6-methoxy-4-chromanone, 6-ethoxy-4-chromanone, 6-benzyloxy-4-chromanone, 6-hydroxy-4-chromanone, 6-carboxy-4-chromanone, 6-acetyl-4-chromanone, 6-benzoyl-4-chromanone, 6-acetoxy-4-chromanone, 6-methoxycarbonyl-4-chromanone, 6-tert-butoxycarbonyl-4-chromanone, 6-benzyloxycarbonyl-4-chromanone, 8-ethyl-4-chromanone, 8-phenyl-4-chromanone, 8-cyclohexyloxy-4-chromanone, 8-benzyloxy-4-chromanone, 8-hydroxy-4-chromanone, 8-carboxy-4-chromanone, 8-acetyl-4-hydroxychromanone, 8-benzoyl-4-chromanone, 8-acetoxy-4-hydroxychromanone, 2-phenyl-4-chromanone, 2-isopropyl-4-chromanone, 2-methyl-2-benzyl-4-chromanone, 2-hydroxybutyl-4-chromanone, and the like.
The present polybutadiene composition contains an effective amount of at least one compound of formula (I-1) or (I-2).
The polybutadiene composition of the present invention preferably contains at least one compound selected from the compound of formula (I-1) or (I-2) in an amount of 0.01 part by weight or more, preferably 0.01 part by weight or more, per 100 parts by weight of the polybutadiene type polymer. The upper limit of the amount of the compound of formula (I) is usually 10 parts by weight or less, preferably 5 part by weight or less per 100 parts by weight of the polybutadiene polymer.
Next, a description will be made to a second aspect of the polybutadiene composition, which comprises
(b-1) a polybutadiene type polymer, and
(b-2) a compound of formula (II).
The polybutadiene polymer that may be used in the second aspect of the present invention is the same as described above for the first aspect of the present invention.
Preferred polybutadiene type polymer in (b) is polybutadiene polymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, or styrene-butadiene block copolymer.
More preferred polybutadiene type polymer in (b) is styrene-butadiene block copolymer.
Substituent groups R1 to R8 in the compound of formula (II) will be explained below.
Examples of the alkyl group represented by R1, R2, R4, R5, R6, R7, and R8 include, for example, an alkyl group having about 1 to 6 carbon atoms.
Specific examples thereof include, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 2-ethylbutyl group, a n-pentyl group, a 1-methylpentyl group, a 1,3-dimethylbutyl group, a n-hexyl group, a n-heptyl group, a 1-methylheptyl group, a 3-methylheptyl group, a n-octyl group, a 2-ethylhexyl group, a 1,1,3-trimethyl hexyl group, a 1,1,3,3-tetramethylpentyl group, a nonyl group, a decyl group, a undecyl group, a 1-methylundecyl group, a dodecyl group, a 1,3,3,5,5-hexamethylhexyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, a octadecyl group and the like.
Examples of the alkyl group represented by R9 or R10 include, for example, a (C1-C18)alkyl group. Specific examples thereof include, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 2-ethylbutyl group, a n-pentyl group, a 1-methylpentyl group, a 1,3-dimethylbutyl group, a n-hexyl group, a cyclopentyl group, a cyclohexyl group and the like.
Examples of the alkoxy group represented by R3 include, for example,
a methoxy group, an ethoxy group, a n-propoxy group,
an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxuy group, a t-butoxy group, a 2-ethylbutoxy group, a n-pentyloxy group, a 1-methylpentyloxy group,
a 1,3-dimethylbutyloxy group, a n-hexyloxy group,
a cyclopentyloxy group, a cyclohexyloxy group and the like.
Examples of the phenyl group which may be substituted with an alkyl group (e.g, C1-C3 alkyl group such as methyl, ethyl, propyl or the like) represented by R5, R6, R7 and R8 include, for example, a phenyl group, o-,m-,p-methylphenyl groups, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2-methyl-6-ethylphenyl group, a 4-t-butylphenyl group, a 2-ethylphenyl group, a 2,6-diethylphenyl group or the like.
Examples of the alkenyl group represented by R9 and R10 include, for example, a (C2-C18)alkenyl group such as a 4-methylpent-3-enyl group, 4,8,12-trimethyl-3,7,11-tridecatrienyl group or the like.
Compounds of formula (II), wherein R3 is a hydrogen atom or a hydroxy group are preferred. More preferred compounds are compounds of formula (II), wherein R1, R2, R4, R9, and R10 represent a methyl group and R5, R6, R7 and R8 represent a hydrogen atom.
Specific examples of the compound of formula (II) include, for example, 2,2,5,7,8-pentamethyl-6-hydroxychromane, 2,2,5,7-tetramethyl-6-hydroxychromane, 2,2,7-trimethyl-6-hydroxychromane, 2,2,8-trimethyl-6-hydroxychromane, 2,2-dimethyl-6-hydroxychromane, 2,2,5-trimethyl-7-t-butyl-6-hydroxychromane, 2,2,5-trimethyl-8-t-butyl-6-hydroxychromane, 2,2,7,8-tetramethyl-6-hydroxychromane, 2,2,5,8-tetramethyl-6-hydroxychromane, 2,2-dimethyl-7-t-butyl-6-hydroxychromane, 4-isopropyl-2,2,5-trimethyl-7-t-butyl-6-hydroxychromane, 4-isopropyl-2,2-dimethyl-7-t-butyl-6-hydroxychromane, 2,2-dimethyl-5-t-butyl-6-hydroxychromane, 2,5,7,8-tetramethyl-2-(4-methylpent-3-enyl)-5-hydroxychromane, 2,5-dimethyl-8-t-butyl-2-(4-methylpent-3-enyl)-6-hydroxychromane, 2-methyl-2-(4-methylpent-3-enyl)-6-hydroxychromane, 2,2,5-trimethyl-6-hydroxychromane, xcex1-tocopherol, xcex2-tocopherol, xcex3-tocopherol, xcex4-tocopherol, xcex5-tocopherol, xcex61-tocopherol, xcex62-tocopherol, xcex7-tocopherol, tocol, 2,2,4-trimethyl-4-(hydroxyphenyl)chromane, 2,2,4,6-tetramethyl-4-(3,5-dimethyl-4-hydroxyphenyl)chromane, 2,3,4-trimethyl-2-ethyl-4-(3-nonyl-4-hydroxyphenyl)-7-nonylchromane, 2,3,4-trimethyl-4-(3,5-diethyl-4-hydroxyphenyl)-6-ethylchromane, 2,2,4,6,8-pentamethyl-4-(3,5-dimethyl-4-hydroxyphenyl)chromane, 2,2,4-triethyl-3-methyl-4-(4-hydroxyphenyl)chromane, 2,2,3-trimethyl-3-(4-hydroxyphenyl)chromane, 2,2,3,6-tetramethyl-3-(3,5-dimethyl-4-hydroxtphenyl)chromane, 2,3,4-trimethyl-2-ethyl-3-(3-nonyl-4-hydroxyphenyl)-7-nonylchromane, 2,2,3-trimethyl-3-(3,5-diethyl-4-hydroxtphenyl)-6-ethylchromane, 2,2,3,6,8-pentamethyl-3-(3,5-dimethyl-4-hydroxyphenyl)chromane, 2,2,5-triethyl-3-methyl-3-(4-hydroxyphenyl)chromane, 2,4,4,6-tetramethyl-2-(3,5-dimethyl-4-hydroxyphenyl)chromane, 2,4,4-triethyl-2-(4-hydroxyphenyl)chromane, 2,3,4-trimethyl-4-ethyl-2-(3,5-dimethyl-4-hydroxyphenyl)-7-nonylchromane, 2,4,4-trimethyl-2-(3,5-diethyl-4-hydroxyphenyl)-6-ethylchromane, 2,4,4,7,8-pentamethyl-2-(3,5-dimethyl-4-hydroxyphenyl)-6-ethylchromane, 2,2,5,7,8-pentamethylchromane, and the like.
The polybutadiene composition of the second aspect of the present invention usually contains an effective amount of the compound of formula (II).
The amount of the compound of formula (II) is preferably 0.001 part by weight or more per 100 parts by weight of the polybutadiene polymer. Any amount of the compound of formula (II) may be used unless subsequent melting and molding of the composition is not adversely affected. The upper limit of the amount of the compound of formula (II) is preferably 10 parts or less, more preferably 5 parts or less per 100 parts by weight of the butadiene polymer.
A description will be made to a third aspect of the polybutadiene composition, which comprises (c-1) a styrene-butadiene copolymer, and (c-2) a benzoin compound.
The styrene-butadiene copolymer is preferably a styrene-butadiene block copolymer.
Examples of the benzoin compound include, a compound of formula (III):
wherein Ar1 and Ar2 are the same or different and independently represent a phenyl group which may be substituted with at least one group selected from the group consisting of a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an alkoxyalkyl group, an aryl group, an arylalkyl group, an aryloxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an arylcarbonyloxy group, and a group of formula: xe2x80x94COOQ, wherein Q represents a hydrogen atom or an alkyl group, and two adjacent substituent groups on the phenyl group together with the carbon atoms to which they are bonded may form a benzene ring or rings.
A description will be made to the substituent groups on the phenyl groups as below.
Examples of the halogen atom include a fluorine atom, a chlroline atom, a bromine atom, an iodine atom.
Examples of the alkyl group include a (C1-C8)alkyl group. Specific examples thereof include, for example, a heptyl group, and octyl group in addition to those specified (C1-C6)alkyl groups in the first aspect of the invention.
Examples of the alkoxy group include, for example, a heptyloxy group, an octyloxy group, in addition to those specified (C1-C6) alkoxy groups in the first aspect of the invention,
Examples of the aryl group include, for example, a phenyl group, a naphthyl group, anthracenyl group and the like.
Examples of the aryloxy group include, for example, a phenoxy group, a naphthyloxy group, anthracenyloxy group and the like.
Examples of the arylalkyl group include, a benzyl group, 1-, or 2-phenethyl group, naphthylmethyl group and the like.
Examples of the alkylcarbonyloxy group include those as specified in the first aspect of the invention.
Examples of the alkylsulfonyloxy group include, for example, methylsulfonyloxy group and the like.
Examples of the arylcarbonyloxy group include, for example, a phenylcarbonyloxy group, a naphthylcarbonyloxy group, an anthracenylcarbonyloxy group and the like
Examples of the alkyl group represented by Q include, for example, the same (C1-C6)alkyl group as described in the first aspect of the invention.
Examples of the Ar1 and Ar2 groups, when two adjacent substituent groups on the phenyl group together with the carbon atoms to which they are bonded form a benzene ring or rings, include, for example, a naphthalene or anthracene.
Preferred benzoin compounds include, for example, a compound of formula (III), wherein Ar1 and Ar2 are the same or different and independently represent a phenyl group, which may be substituted with an alkyl group, an alkoxy group or an alkoxyalkyl group.
Examples of the alkyl group include, for example, a (C1-C6)alkyl group. Specific examples thereof include, for example, those specific alkyl groups as described in the first aspect of the invention.
Examples of the alkoxy group include, for example, a (C1-C6)alkoxy group. Specific examples thereof include, for example, those alkoxy groups as described in the first aspect of the invention.
Examples of the alkoxyalkoxy group include, for example, an alkoxyalkoxy group having 2 to 6 carbon atoms. Specific examples thereof include methoxymethoxy group or the like.
Specific examples of the benzoin compound include, for example, 3xe2x80x2-hydroxybenzoin, 4,4xe2x80x2-dimethoxybenzoin, 4,4xe2x80x2-bis(methoxymethoxy)benzoin, 4xe2x80x2-methylbenzoin, 4xe2x80x2-ethylbenzoin, 4xe2x80x2-n-propylbenzoin, 4xe2x80x2-isopropylbenzoin, 4xe2x80x2-n-butylbenzoin, 4xe2x80x2-sec-butylbenzoin, 4xe2x80x2-t-butylbenzoin, 4xe2x80x2-amylbenzoin, 4xe2x80x2-hexylbenzoin, 4xe2x80x2-heptylbenzoin, 4xe2x80x2-octylbenzoin, 4xe2x80x2-fluorobenzoin, 4xe2x80x2-chlorobenzoin, 4xe2x80x2-bromobenzoin, 4xe2x80x2,4-difluorobenzoin, 4xe2x80x2,4-dichlorobenzoin, 4xe2x80x2,4-dibromobenzoin, 4-methoxybenzoin, 4xe2x80x2-phenoxybenzoin, 4xe2x80x2-phenylbenzoin, 4xe2x80x2-cyclohexylbenzoin, 2xe2x80x2,4xe2x80x2,6xe2x80x2-trimethylbenzoin, 9,9xe2x80x2-anthroin, 2-hydroxy-1,2-di-(1-naphthyl)ethanone and the like.
The polybutadiene composition of the third aspect of the present invention usually contains an effective amount of the benzoin compound of formula (III). The amount of the benzoin compound is preferably 0.01 part, more preferably 0.05 part by weight or more per 100 parts by weight of the styrene-butadiene copolymer, and preferably 10 parts by weight, more preferably 5 parts by weight per 100 parts by weight of the styrene-butadiene copolymer.
The polybutadiene compositions of the present invention may optionally comprise an antioxidant such as phenol antioxidants, sulfur antioxidants, phosphorous antioxidant or the like.
Examples of the phenol antioxidant include, for example,
(1) alkylated monophenols such as 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(xcex1-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1xe2x80x2-methylundecyl-1xe2x80x2-yl)phenol, 2,4-dimethyl-6xe2x80x2-(1xe2x80x2-methylheptadecyl-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methyltridecyl-1xe2x80x2-yl)phenol and a mixture thereof;
(2) alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol and a mixture thereof;
(3) hydroquinones and alkylated hydroquinones such as 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, bis(3,5-di-t-butyl-4-hydroxyphenyl)adipate and a mixture thereof;
(4) hydroxylated thiodiphenyl ethers such as 2,2xe2x80x2-thiobis(6-t-butylphenol), 2,2xe2x80x2-thiobis(4-methyl-6-t-butylphenol), 2,2xe2x80x2-thiobis(4-octylphenol), 4,4xe2x80x2-thiobis(3-methyl-6-t-butylphenol), 4,4xe2x80x2-thiobis(2-methyl-6-t-butylphenol), 4,4xe2x80x2-thiobis(3,6-di-t-amylphenol), 4,4xe2x80x2-(2,6-dimethyl-4-hydroxyphenyl)disulfide and the like;
(5) alkylidenebisphenols and derivative thereof such as 2,2xe2x80x2-methylenebis(4-methyl-6-t-butylphenol), 2,2xe2x80x2-methylenebis(4-ethyl-6-t-butylphenol), 2,2xe2x80x2-methylenebis[4-methyl-6-(xcex1-methylcyclohexyl)phenol]], 2,2xe2x80x2-methylenebis(4-methyl-6-cyclohexylphenol), 2,2xe2x80x2-methylenebis(4-methyl-6-nonylphenol), 2,2xe2x80x2-methylenebis(4,6-di-t-butylphenol)], 2,2xe2x80x2-ethylidenebis(4,6-di-t-butylphenol), 2,2xe2x80x2-ethylidenebis(4-isobutyl-6-t-butylphenol), 2,2xe2x80x2-methylenebis[6-(xcex1-methylbenzyl)-4-nonylphenol], 2,2xe2x80x2-methylenebis[6-(xcex1,xcex1-dimethylbenzyl)-4-nonylphenol], 4,4xe2x80x2-methylenebis(6-t-butyl-2-methylphenol), 4,4xe2x80x2-methylenebis(2,6-di-t-butylphenol), 4,4xe2x80x2-butylidenebis(3-methyl-6-t-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis[3-t-butyl-5-methyl-2-hydroxybenzyl]-4-methylphenol, 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, bis[3,3-bis-3xe2x80x2-t-butyl-4xe2x80x2-hydroxyphenyl]butyrate], bis(3-t-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3xe2x80x2-t-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylbenzyl)-6-t-butyl-4-methylphenyl]tere phthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-t-butyl-4-hydroxy-2-methylphenyl)pentane, 2-t-butyl-6-(3xe2x80x2-t-butyl-5xe2x80x2-methyl-2xe2x80x2-hydroxybenzyl)-4-methylphenyl-acrylate, 2,4-di-t-pentyl-6-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]phenyl acrylate and a mixture thereof;
(6) O-, N- and S-benzyl derivatives such as 3,5,3xe2x80x2,5xe2x80x2-tetra-t-butyl-4,4xe2x80x2-dihydroxydibenzyl ether, octadodecyl-4-hydroxy-3,5-dimethylbenzylmercapto acetate, tris(3,5-di-t-butyl-4-hydroxybenzyl)amine, bis(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-t-butyl-4-hydroxybenzylmercapto acetate and a mixture thereof;
(7) hydroxybenzylated malonate derivatives such as dioctadecyl-2,2-bis(3,5-di-t-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-t-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate and a mixture thereof;
(8) aromatic hydroxybenzyl derivatives such as 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,4-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)phenol and a mixture thereof;
(9) triazine derivatives 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-t-butylphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-t-butyl-4-hydroxy)-1,3,5-triazine, tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl isocyanurate, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenylpropyl)-1,3,5-triazine, tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, tris[2-(3xe2x80x2,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxycinnamoyloxy)ethyl]-isocyanurate and a mixture thereof;
(10) benzyl phosphonate derivatives such as dimethyl-3,5-di-t-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-3,5-di-t-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzyl phosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzyl phosphonic acid monoester and a mixture thereof;
(11) acylaminophenol derivatives such as anilide 4-hydroxylaurate, anilide 4-hydroxystearate, octyl-N-(3,5-di-t-butyl-4-hydroxyphenyl)carbanate and a mixture thereof;
(12) esters of xcex2-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid and the following monohydric or polyhydric alcohol: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane and a mixture thereof;
(13) esters of xcex2-(5-t-butyl-4-hydroxy-3-methylphenyl)propionic acid and the following monohydric or polyhydric alcohol: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane and a mixture thereof;
(14) esters of xcex2-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid and the following monohydric or polyhydric alcohol: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane and a mixture thereof;
(15) esters of 3,5-di-t-butyl-4-hydroxyphenylacetic acid and the following monohydric or polyhydric alcohol: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane and a mixture thereof; and
(16) amides of xcex2-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid such as N,Nxe2x80x2-bis[3-(3xe2x80x2,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxyphenyl)propionyl]hydrazine, N,Nxe2x80x2-bis[3-(3xe2x80x2,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxyphenyl)propionyl]hexamethylenediamine, N,Nxe2x80x2-bis[3-(3xe2x80x2,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxyphenyl)propionyl]-trimethylenediamine and a mixture thereof.
Phenol antioxidants such as those mentioned above can be used singly or as a combination of two or more of them.
Examples of the phosphorous antioxidant include: triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-t-butylphenyl)pentaerythritol diphosphate, tristearyl sorbitol triphosphite, tetrakis(2,4-di-t-butylphenyl)-4,4xe2x80x2-diphenylene diphosphite, 2,2xe2x80x2-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, 2,2xe2x80x2-ethylidenebis(4,6-di-t-butylphenyl)fluoro phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, bis(2,4-di-t-butyl-6-methylphenyl)methyl phosphite, (2,4,6-tri-t-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxaphosphorinane, 2,2xe2x80x2,2xe2x80x3-nitrilo[triethyl-tris(3,3xe2x80x2,5,5xe2x80x2-tetra-t-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-diyl)phosphite and a mixture thereof.
Phosphorous antioxidants such as those mentioned above can be used singly or as a combination of two or more of them.
Examples of the Sulfur Antioxidant Include:
dilauryl 3,3xe2x80x2-thiodipropionate, tridecyl 3,3xe2x80x2-thiodipropionate, dimyristyl 3,3xe2x80x2-thiodipropionate, distearyl 3,3xe2x80x2-thiodipropionate, lauryl stearyl 3,3xe2x80x2-thiodipropionate, neopentanetetraylkis(3-lauryl thiopropionate) and a mixture thereof.
Sulfur antioxidants described above can be used singly or as a combination of two or more of them.
The antioxidants as described above may be comprised in an amount of 0.001 part by weight or more in the polybutadiene composition of the present invention based on 100 parts by weight of the polybutadiene composition. From economical view point, the amount is preferably 10 parts by weight or less based on 100 parts by weight of the polybutadiene composition.
The polybutadiene composition of the present invention may further comprise other additives such as an ultraviolet absorber, a photostabilizer, a hydroxylamine, a metal inactivating agent, a lubricant, a metal soap, a nucleating agent, an antistatic agent, a flame retardant, a pigment, a filler and the like.
Examples of the Ultraviolet Absorbers Include
(1) salicylate derivatives such as phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3xe2x80x2,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxybenzoate, 4-octylphenyl salicylate, bis(4-t-butylbenzoyl)resorcinol, benzoylresorcinol, hexadecyl 3xe2x80x2,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxybenzoate, octadecyl 3xe2x80x2,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl 3xe2x80x2,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxybenzoate and a mixture thereof;
(2) 2-hydroxybenzophenone derivatives such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2xe2x80x2-dihydroxy-4-methoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2xe2x80x2,4,4xe2x80x2-tetrahydroxybenzophenone and a mixture thereof; and
(3) 2-(2xe2x80x2-hydroxyphenyl)benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-t-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(5xe2x80x2-t-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-5xe2x80x2-t-octylphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-s-butyl-2xe2x80x2-hydroxy-5xe2x80x2-t-butylphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-4xe2x80x2-octyloxypheny)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-t-amyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-[2xe2x80x2-hydroxy-3xe2x80x2,5xe2x80x2-bis(xcex1, xcex1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-[(3xe2x80x2-t-butyl-2xe2x80x2-hydroxyphenyl)-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3xe2x80x2-t-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)carbonylethyl]-2xe2x80x2-hydroxyphenyl]-5-chlorobenzotriazole 2-[3xe2x80x2-t-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)-phenyl]-5-chlorobenzotriazole, 2-[3xe2x80x2-t-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl]benzotriazole, 2-[3xe2x80x2-t-butyl-2xe2x80x2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl]benzotriazole, 2-[3xe2x80x2-t-butyl-2xe2x80x2-hydroxy-5xe2x80x2-[2-(2-ethylhexyloxy)carbonyl-ethyl]phenyl]-benzotriazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidemethyl)-5-methylphenyl]-benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, a mixture of 2-(3xe2x80x2-dodecyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)benzotriazole and 2-[3xe2x80x2-t-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-isooctyloxycarbonylethyl)phenyl]benzotriazole, 2,2xe2x80x2-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2xe2x80x2-methylenebis[4-t-butyl-6-(2H-benzotriazol-2-yl)phenol], a condensate of poly(3-11)(ethylene glycol) and 2-[3xe2x80x2-t-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl]benzotriazole, a condensate of poly(3-11)(ethylene glycol) and methyl 3-[3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]propionate, 2-ethylhexyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, octyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, methyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxy-phenyl]propionic acid, and a mixture thereof.
The ultraviolet absorbers such as those mentioned above can be used singly or as a combination of two or more of them.
Examples of the Photo Stabilizer Include
(1) hindered amine photo stabilizers such as bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(N-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-acrolyl-2,2,6,6-tetramethyl-4-piperidyl)2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl decanedioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetarkis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butaneteracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butantetracarboxylate,
a mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol,
a mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol,
a mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane,
a mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane,
a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine,
poly[(6-morpholino-1,3,5-triazin-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], poly[(6-(1,3,3-tetramethylbutyl)imino-1,3,5-triazin-2,4-diyl((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-peperidyl)imino)],
a polycondensate of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 1,2-dibromoethane,
N,Nxe2x80x2,4,7-tetrakis[4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)-amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10 diamine, N,Nxe2x80x2,4-tris[4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10 diamine, N,Nxe2x80x2,4,7-tetrakis[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10diamine, N,Nxe2x80x2,4-tris[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, and a mixture thereof;
(2) acrylate photostabilizers such as ethyl xcex1-cyano-xcex2,xcex2-diphenylacrylate, isooctyl xcex1-cyano-xcex2,xcex2-diphenylacrylate, methyl xcex1-carbomethoxycinnamate, methyl xcex1-cyano-xcex2-methyl-methoxycinnamate, butyl xcex1-cyano-xcex2-methyl-p-methoxycinnamate, methyl xcex1-carbomethoxy-p-methoxycinnamate, N-(xcex2-carbomethoxy-xcex2-cyanovinyl)-2-methylindoline and a mixture thereof;
(3) nickel photostabilizers such as nickel complex of 2,2xe2x80x2-thiobis-[4-(1,1,3,3-tetramethylbutyl)phenol], nickel dibutyldithiocarbamate, nickel salt of monoalkyl ester, nickel complex of ketoxime and a mixture thereof;
(4) oxamide photostabilizers such as 4,4xe2x80x2-dioctyloxyoxanilide, 2,2xe2x80x2-diethoxyoxanilide, 2,2xe2x80x2-dioctyloxy-5,5xe2x80x2-di-t-butylanilide, 2,2xe2x80x2-didodecyloxy-5,5xe2x80x2-di-t-butylanilide, 2-ethoxy-2xe2x80x2-ethyloxanilide, N,Nxe2x80x2-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-t-butyl-2xe2x80x2-ethoxyanilide, 2-ethoxy-5,4xe2x80x2-di-t-butyl-2xe2x80x2-ethyloxanilide and a mixture thereof; and
(5) 2-(2-hydroxyphenyl)-1,3,5-triazine photostabilizers such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and a mixture thereof.
Examples of the hydroxylamine include, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N,N-dibenzylhydroxylamine, N,N-dibenzylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine and a mixture thereof.
Examples of the metal inactivating agent include, for example, N,Nxe2x80x2-diphenyloxamide, N-salicylal-Nxe2x80x2-salicyloylhydrazine, N,Nxe2x80x2-bis(salicyloyl)hydrazine, N,Nxe2x80x2-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxalinide, isophthaloyl dihydrazide, sebacoylbisphenyl hydrazide, N,Nxe2x80x2-bis(salicyloyl)thiopropionyl dihydrazide and a mixture thereof.
Examples of the lubricant include, for example, an aliphatic hydrocarbon such as paraffin or wax, higher aliphatic acid having 8 to 22 carbon atoms, higher aliphatic acid (having 8 to 22 carbon atoms) metal (Al, Ca, Mg, Zn) salt, aliphatic alcohol having 8 to 22 carbon atoms, polyglycol, ester of higher fatty acid having 4 to 22 carbon atoms and aliphatic monohydric alcohol having 4 to 18 carbon atoms, higher aliphatic amide having 8 to 22 carbon atoms, silicone oil, rosin derivative and the like.
The polybutadiene composition of the present invention can be produced, for example, by melt-kneading the polybutadiene type polymer and the compound (I-1), compound (I-2), compound (II) or the benzoin compound. More specifically, it can be produced by adding any one of the compounds as listed above to the melt-kneaded polybutadiene type polymer, followed by further melt-kneading, thereby the compound is uniformly dispersed in the polybutadiene composition, or by blending the polybutadiene type polymer and the compound and optionally further additives to obtain a composition, met-kneading the same and extruding the melted composition. Alternatively, the compound can be added while the polymerization reaction for producing the polybutadiene type polymer is under progress or immediately after the end of the polymerization reaction. The compound may be added as a solid state or as a solution of the compound in a solvent.
When an antioxidant and/or another additive are added to the composition, the compound may also be added at the same time. When they are added at the same time, the compound may be dissolved in a heat-melted antioxidant and/or other additive. If the antioxidant and/or other additive are in liquid state, the compound may be dissolved or dispersed in them.
The present composition thus produced is typically melted at 150xc2x0 C. or higher, preferably 170xc2x0 C. or higher. The upper limit of the temperature is set within such a temperature range where decomposition of the polybutadiene polymer and the compound does not occur, and is typically 250xc2x0 C. or lower, preferably 220xc2x0 C. or lower.
Production of the molded articles from the composition of the present invention can be accomplished by a conventional method such as injection molding, extruding molding, blow molding or the like.
The appearances of the articles molded from the present polybutadiene composition such as hoses, footwear, toys, films and various vessels produced by various molding methods such as injection molding, extruding, blow molding or the like, is improved.

Abstract: a polybutadiene type polymer, and

Abstract: at least one compound selected from

Abstract: a compound of formula (I-1):

Abstract: or a compound of formula (I-2):

Abstract: wherein R11 to R28 are the same or different and independently represent a hydrogen atom, an alkyl group, or the like; or

Abstract: a compound of formula (II):

Abstract: wherein R1 to R10 independently represent a hydrogen atom, an alkyl group, or the like; or

Abstract: a styrene-butadiene copolymer, and a benzoin compound; and an article molded therefrom, and processes for producing the composition and the molded article.


To provide a de-interleave circuit used for a BS digital broadcasting receiver. The de-interleave circuit is provided with less memory. An address data generator (3) supplies address data (A) to a de-interleave memory (4) in a de-interleave order. Each main signal is read from an address location in the de-interleave memory (4) specified by address data (A), and a following main signal is interleaved and written in that address location of the memory. As a result, the de-interleave memory (4) only requires space for one superframe.

The present invention relates to a de-interleave circuit used for a BS digital broadcasting receiver.
As is already known, an interleave system in a BS digital broadcasting receiver performs block interleave, 8xc3x97203 bytes in terms of bytes, interleaving between slots with a same slot number in each frame in the superframe direction.
Here, an MPEG2-TS bucket of a main signal of a BS digital broadcasting signal comprises 1 slot made up of 204 bytes, 203 bytes including parity 16 bytes for correction of external code errors plus 1 byte of a TMCC (Transmission and Multiplexing Configuration Control) signal to indicate a synchronization signal, modulation system and error correction system, etc., with 48 slots forming 1 frame and 8 frames forming 1 superframe.
De-interleaving data interleaved as shown above requires a memory with a storage capacity for 2 superframes. This requires a memory with a storage capacity of a maximum of 155904 bytes (=203 (bytes)xc3x9748 (slots)xc3x978 framesxc3x972 (superframes)).
However, configuring a conventional de-interleave circuit using a memory with a storage capacity amounting to 2 superframes involves such a problem that the number of gates increases when the de-interleave circuit is implemented with an integrated circuit and at the same time the chip area increases.
It is an object of the present invention to provide a de-interleave circuit that requires less memory.
The de-interleave circuit according to the present invention is a de-interleave circuit in a BS digital broadcasting receiver provided with address data generating means that generates address data A, in which assuming that the number of main signals in 1 slot is m, the depth of de-interleave is n, a specific address number assigned to a de-interleave memory is y, address data that specifies a data read/write address location is A, a modulo b is a remainder of axe2x88x92xcex1b (xcex1: a natural number including 0),
when (yxe2x89xa0nxc3x97mxe2x88x921), A=yxc3x97n to the xth power modulo (nxc3x97mxe2x88x921), and
when (y=nxc3x97mxe2x88x921), A=y,
address set number x, which is the number of times data of up to address number y is repeatedly specified, is such an x that when y=1, A=1 in A=yxc3x97n to the xth power modulo (nxc3x97mxe2x88x921) and
when the value of yxc3x97n to the xth power is less than (nxc3x97mxe2x88x921), A=(yxc3x97n to the xth power), and is characterized in that the main signal stored in the address location in a memory specified by the address data generated by the address generating means is read and the following main signal, which is interleaved and input, is written in that address location.
In the de-interleave circuit according to the present invention, the main signal stored in the address location in memory specified by address data A generated by the address generating means is read. Since the following main signal, which is interleaved and input, is written in the address location, which has been substantially emptied by the aforementioned read, de-interleave can be performed with a storage capacity for a de-interleave memory and the de-interleave memory requires a storage capacity only xc2xd of the conventionally required storage capacity of 2 superframes, which means that the required area is reduced when the circuit is implemented with an integrated circuit.
In the de-interleave circuit according to the present invention, the address data generating means is provided with:
a base-m counter that counts the number of main signals input;
a base-S counter that counts a carry of the base-m counter;
a multiplier that multiplies the count value of the base-S counter by (nxc3x97m);
offset value counting means that counts the number of main signals in the slot direction, shifts by one stage in the n direction when the main signal count value reaches (mxe2x88x921) and counts main signals in the slot direction, and continues to count by repeating this procedure until the count value reaches (nxc3x97m); and
adding means that adds up the output of the multiplier and the count value of the offset value counting means, and is characterized in that the output of the adding means is deemed as address data A.
De-interleave is performed by reading a main signal from the address location in a memory specified by the address data output from the address generating means and writing the main signal.


The present application discloses a display panel, a repair method for the display panel and a display device, where a repair line includes a first repair point, a second repair point and a third repair point which overlap with a data line, the first repair point is located on a side of a first overlapping area away from the second repair point, the second repair point is located between the first overlapping area and a second overlapping area, and the third repair point is located on a side of the second overlapping area away from the second repair point.

The statements herein merely provide background information related to the present application and do not necessarily constitute the conventional art. With the development and advancement of science and technology, display panel has become the mainstream of display products due to its thin body, low power consumption and low radiation, and has been widely used. Display panel includes a Thin Film Transistor-Liquid Crystal Display (TFT-LCD). TFT-LCD refracts light rays of backlight modules to generate pictures by controlling the rotation direction of liquid crystal molecules, and has many advantages, such as thin body, low power consumption, and no radiation and the like.
In the manufacturing process of the display panel, due to environment or machine equipment factors, a short circuit often occurs in an overlapping area of the data lines and the scanning lines, or a short circuit often occurs in an overlapping area of the data lines and the common electrodes, so that the product yield is reduced, and the cost is wasted.

Display panel, repair method for display panel and display device

CHONGQING HKC OPTOELECTRONICS TECHNOLOGY CO., LTD.


A method for fabricating a semiconductor device includes etching a substrate to form trenches that separate active regions, forming an insulation layer having an opening to open a portion of a sidewall of each active region, forming a silicon layer pattern to gap-fill a portion of each trench and cover the opening in the insulation layer, forming a metal layer over the silicon layer pattern, and forming a metal silicide layer as buried bit lines, where the metal silicide layer is formed when the metal layer reacts with the silicon layer pattern.

Exemplary embodiments of the present invention relate to a method for fabricating a semiconductor device, and more particularly, to a method for fabricating a semiconductor device with buried bit lines.
As the degree of integration for Dynamic Random Access Memory (DRAM) devices increases, two-dimensional (2D) structures are reaching limits. Thus, three-dimensional (3D) DRAMs with vertical gates (VG), which are referred to hereinafter as VG DRAM, are being developed.
A 3D DRAM having a vertical gate structure may include active regions, each of which is formed of a body and a pillar formed over the body, buried bit lines BBL, and vertical gates VG. The bodies of adjacent active regions are separated from each other by a trench and the buried bit lines BBL are formed within the trenches. Each buried bit line BBL is electrically connected with a sidewall of each active region. Each vertical gate VG is formed on one sidewall of a pillar over a buried bit line BBL, and a source and a drain are formed within the pillar. The vertical gate VG is used for formation of a vertical channel between the source and the drain.
In order to drive a cell in a buried bit line BBL, a One-Side-Contact (OSC) process may be used. The one-side contact process may be also referred to as a Single-Side-Contact (SSC). The one-side contact process is a process for forming a contact in an active region while insulating the active region from adjacent active regions.
Since bit lines have a buried structure in the three-dimensional DRAM having a vertical gate structure, the area of the buried bit lines BBL is limited. Therefore, a metal layer may be used to form the buried bit lines BBL with a low bit line resistance. In order to fill a metal layer in deep trenches without void, a Chemical Vapor Deposition (CVD) process or an Atomic Layer Deposition (ALD) process may be used.
Buried bit lines BBL may be formed of a titanium nitride (TiN) layer and a tungsten (W) layer. The titanium nitride (TiN) layer and the tungsten (W) layer are deposited through the CVD process.
Here, when the line width of the buried bit lines BBL is decreased, drastic resistance increase may occur because the area occupied by tungsten (W) in the buried bit lines BBL is decreased while the thickness of the titanium nitride (TiN) layer remains the same.
Since the CVD process results in rough surfaces of the tungsten layer, void and seam may be created.
When a subsequent etch-back process is performed to acquire a desired bit line height, the buried bit lines BBL may be cut undesirably or punctured all the way through to the lower substrate and thus defective semiconductor device products may result.

Method for fabricating semiconductor device with buried bit lines


An electrolysis device is configured such that water flowing into a container from an inlet flows from an upstream side to a downstream side in the container and flows out from an outlet. A first electrode pair is arranged on the upstream side than a second electrode pair. In the electrolysis device, in order to suppress a decrease in current density due to electrolyte concentration in the water in the second electrode pair arranged on the downstream side than the first electrode pair, the current density in the second electrode pair is adjusted.

In general, a heat-pump-type water heater includes a refrigerant circuit in which a compressor, a water heat exchanger, an expansion valve, and an air heat exchanger are connected by pipes in this order; and a hot water storage circuit including a tank in which water is stored, an inflow water pipe for feeding the water in the tank to the water heat exchanger, and an outflow hot water pipe for returning the water heated by the water heat exchanger to the tank. In the heat-pump-type water heater, usually, a water supply source of the water stored in the tank is tap water, well water, or the like.
Incidentally, the tap water or the well water contains components such as calcium ion, magnesium ion, and the like that cause scale (hereinafter referred to as scale components). Therefore, in a water heater, scale of calcium salt, magnesium salt, and the like is precipitated. In particular, underground water such as the well water has high concentration of the scale components compared with the tap water and has water quality that tends to cause scale. In the water heat exchanger, since the temperature of the water is high, scale is more likely to be precipitated than in other regions. When scale is precipitated and deposited on the inner surface of a pipe of the water heat exchanger, a problem occurs in that, for example, the heat transfer performance of the water heat exchanger is deteriorated or a channel of the pipe is narrowed.
For example, Patent Document 1 proposes a cooling water circulating apparatus including an electrolysis device in which one electrode pair is set in an electrolytic cell. Patent Document 1 describes that, since scale components can be removed from cooling water through electrolysis, it is possible to reduce adhesion of scale in a circulating path.
However, in the electrolysis device disclosed in Patent Document 1, removal efficiency for scale components in water is not necessarily sufficient.
Patent Document 1: WO2006/027825

Electrolysis device and heat-pump-type water heater provided with same


A medical imaging system with a screen, an X-ray imaging device having an X-ray interface and an intravascular data acquisition device having an intravascular interface provide enhanced X-ray images. For this purpose, the medical imaging system is adapted for overlaying an information set provided at the intravascular interface onto an X-ray image provided at the X-ray interface on user request for generating an enhanced X-ray image and for displaying the enhanced X-ray image on the screen.

For the evaluation and intervention of Coronary Artery Disease (CAD), the use of different medical modalities is known. X-ray, as one of the common modalities, is in use for the diagnosis of CAD and for guidance in interventional procedures. Thereby, X-ray images may provide a silhouette of the vessel lumen. For enhancing the information about a lesion, non-angiographic coronary lesion assessment tools or intravascular technologies, respectively, like intravascular ultrasound (IVUS), optical coherence tomography (OCT), fractional flow reserve (FFR), near-infrared spectroscopy (NIRS) and other tools may also be used in order to gather more information about the internal structure and function of the vessel and the plaque/tissue characteristics. Since from a technical imaging perspective, there is no direct relation between the information of the X-ray image data (i.e. global information) and intravascularly gathered data (i.e. local information), mental correlation of these two sets of data is necessary for a cardiologist.

Medical imaging system and method for providing an enhanced X-ray image


A structure of a polysilicon via that includes a semiconductor substrate, a conducting layer on the substrate, a dielectric layer on the conducting layer, a polysilicon plug formed in the dielectric layer, a polysilicon layer on the polysilicon plug, and a silicide layer formed on the polysilicon layer. The polysilicon layer is electrically connected to the conducting layer through the polysilicon plug. The structure of a polysilicon via according to the invention prevents the occurrence of leakage currents in the presence of misalignment in the follow-up photolithography process.

1. Field of the Invention
This invention relates to a semiconductor device and, more particularly, to a structure of a polysilicon via of a dynamic random access memory (DRAM).
2. Description of Related Art
A polysilicon via is generally used in a capacitor-over-bit-line (COB) dynamic random access memory (DRAM) to connect a bit line and the source/drain regions on the substrate. Conventionally, a polysilicon via consists of a polysilicon layer and a silicide layer, wherein the polysilicon layer is used to control the resistance over the bit line, wherein the resistance of the bit line is proportional to the thickness of the polysilicon layer of the polysilicon via. Even though having a lower resistance over the bit line provides a better data transmission rate, the thickness of the polysilicon layer of the polysilicon via is usually made to provide a reasonable conductivity while also downsizing the device to fit within a limited space. However, a conventional polysilicon via lacks protection against the occurrence of misalignment in the follow-up photolithography process. That is, the conventional polysilicon via is easily etched through in the presence of misalignment. The conducting layer underneath the polysilicon layer could be damaged by the etching process, and that further causes the occurrence of leakage currents, which degrade the performance of a DRAM cell.
The fabricating process of a conventional polysilicon via is shown in FIGS. 1A through 1C.
Referring to FIG. 1A, a dielectric layer, of borophosphosilicate glass (BPSG), 30 is deposited on a polysilicon layer 20 by performing a chemical vapor deposition process, wherein the polysilicon layer 20 is formed on a provided substrate 10. By performing a photolithography process and an anisotropic etching process, a via hole 40 is formed to expose the polysilicon layer 20.
Referring next to FIG. 1B, sequentially, a polysilicon layer 50 and a tungsten silicide layer 60 are both deposited on the BPSG layer 30 and in the via hole 40 by low-pressure chemical vapor deposition processes. The thickness of the polysilicon layer 50 is about 500 to 1000 .ANG., and the thickness of the tungsten silicide layer 60 is about 1000 to 1500 .ANG..
Referring to FIG. 1C, the tungsten silicide layer 60 and the polysilicon layer 50 are etched to form a bit line 70 and a polysilicon via of a DRAM. Because the polysilicon via is hollow, the width of patterned bit line 70 is wider than the width of the via hole 40 to ensure the conductivity of the bit line 70. The border layout of the bit line increases the difficulty of the bit-line layout.
Because the polysilicon layer 20 is only covered by the polysilicon layer 50 and the tungsten silicide layer 60, once a situation of misalignment happens in a follow-up photolithography process, the polysilicon via or the bit line 70 is etched through, which further causes damage to the polysilicon layer 20 underneath. The damage to the polysilicon layer 20 leads to the occurrence of leakage current that degrades the performance and efficiency of a COB DRAM cell.
The width of the bit line 70 on the via hole 40 is made to be wider than the width of the via hole 40 to reduce the damage caused by misalignment. However, the widened bit line on the via hole 40 further increases the difficulty of the layout of a DRAM bit line.


An image display apparatus according to the present invention, includes a light emitter, a first panel configured to transmit light emitted from the light emitter, a second panel configured to transmit light transmitted through the first panel, and a controller configured to control emission brightness of the light emitter and at least one of transmittance of the first panel and transmittance of the second panel, based on input image data.

Field of the Invention
The present invention relates to an image display apparatus and a control method thereof.
Description of the Related Art
Recently improvements in the visibility of display images (images displayed on a screen) are demanded for image display apparatuses. Specifically, an increase in the ratio between the bright part and the dark part (contrast ratio) of display images is demanded for image display apparatuses.
A prior art on the image display apparatus is disclosed, for example, in Japanese Patent Application Laid-Open No. 2010-107535 and Japanese Patent Application Laid-Open No. 2008-122536.
Japanese Patent Application Laid-Open No. 2010-107535 discloses a liquid crystal display apparatus having a liquid crystal panel and a backlight unit. In the liquid crystal display apparatus disclosed in Japanese Patent Application Laid-Open No. 2010-107535, the transmittance of the liquid crystal panel in the bright part display region and the emission brightness of the backlight unit in the bright part display region are increased. Further, the transmittance of the liquid crystal panel in the dark part display region and the emission brightness of the backlight unit in the dark part display region are decreased. The bright part display region is a region where bright parts of the image are displayed, out of the regions on the screen, and the dark part display region is a region where dark parts of the image are displayed, out of the regions on the screen. A control to partially change the emission brightness of the backlight unit is called "local dimming control".
However, the minimum size of a region where the emission brightness can be changed by the local dimming control is larger than the size of the liquid crystal element of the liquid crystal panel. Therefore, if an image having many high frequency components (e.g. an image having many fine edges) is displayed, the contrast ratio of the display image is not improved very much even if the local dimming control is performed.
Japanese Patent Application Laid-Open No. 2008-122536 discloses a liquid crystal display apparatus having a color liquid crystal panel, a monochrome liquid crystal panel, and a backlight unit. The backlight unit emits light at a predetermined emission brightness. The monochrome liquid crystal panel is disposed between the color liquid crystal panel and the backlight unit, and the light emitted from the backlight unit transmits through the monochrome liquid crystal panel, and then transmits through the color liquid crystal panel. In the liquid crystal display apparatus disclosed in Japanese Patent Application Laid-Open No. 2008-122536, not only the transmittance of the color liquid crystal panel, but also the transmittance of the monochrome liquid crystal panel is controlled. Thereby the contrast ratio of the display images improves. Such a structure of having the two liquid crystal panels is hereafter called "double panel structure".
The minimal size of the region where the transmittance of the monochrome liquid crystal panel can be changed is the size of the liquid crystal element of the monochrome liquid crystal panel, and is smaller than the minimal size of the region where the emission brightness can be changed by the local dimming control. Therefore in the image display apparatus having the double panel structure, the contrast ratio of the display image can be easily improved, even if the display image includes many high frequency components.
However, in the case of a conventional liquid crystal di splay apparatus having the double panel structure, the emission brightness of the backlight unit is controlled to a higher value than the case of using one liquid crystal panel considering that the light emitted from the backlight unit transmits through the two liquid crystal panels. As a result, in the conventional liquid crystal display apparatus, total power consumption of the liquid crystal apparatus is increased by the use of the double panel structure.

Image display apparatus and control method thereof


A back side illuminated image sensor may be provided with an array of image sensor pixels. Each pixel may include a substrate having a front surface and a back surface. The pixels may have a charge storage region at the back surface and a charge readout node at the front surface of the substrate. The pixels may receive light at the back surface. Photo-generated charge may be accumulated at the charge storage region during a charge integration cycle. Upon completion of the charge integration cycle, a transfer gate formed at the front surface may be pulsed high to move the charge from the charge storage region to the charge readout node using a global shutter algorithm. The pixels may include two reset transistors that are coupled to column feedback amplifier circuitry for mitigating kTC-reset noise when the pixels are operated in a global shutter mode.

This relates to solid-state image sensor arrays and, more specifically, to image sensors with small size pixels that are illuminated from the back side of a pixel substrate. Small pixel sizes reduce the cost of manufacturing image sensor arrays, but it is important not to sacrifice image sensor performance when pixel size is reduced.
Conventional complementary metal-oxide-semiconductor (CMOS) image sensors sense light by converting impinging photons into electrons that are integrated (collected) in sensor pixels. Upon completion of each integration cycle, the collected charge is converted into voltage signals, which are supplied to corresponding output terminals associated with the image sensor. Typically, the charge-to-voltage conversion is performed directly within the pixels, and the resulting analog pixel voltage signals are transferred to the output terminals through various pixel addressing and scanning schemes. The analog voltage signal can sometimes be converted on-chip to a digital equivalent before being conveyed off-chip. Each pixel includes a buffer amplifier (i.e., source follower) that drives output sensing lines that are connected to the pixels via respective address transistors.
After the charge-to-voltage conversion is complete and after the resulting signals are transferred out from the pixels, the pixels are reset before a subsequent integration cycle begins. In pixels that include floating diffusions (FD) serving as the charge detection node, this reset operation is accomplished by momentarily turning on a single reset transistor that connects the floating diffusion node to a voltage reference for draining (or removing) any charge transferred to the FD node. However, removing charge from the floating diffusion node using the reset transistor generates kTC-reset noise, as is well known in the art. This kTC noise must be removed using correlated double sampling (CDS) signal processing techniques in order to achieve desired low noise performance. Typical CMOS image sensors that utilize CDS require at least three transistors (3T) or four transistors (4T) per pixel. An example of the 4T pixel circuit with a pinned photodiode can be found in Lee (U.S. Pat. No. 5,625,210), incorporated herein as a reference.
A cross-sectional side view of a conventional pixel 100 is shown in FIG. 1. Pixel 100 is formed in substrate 101. Pixel substrate 101 includes p+ doped layer 102 deposited on the back surface of pixel substrate 101, which prevents the generation of excessive dark current by interface states. Substrate 101 includes epitaxial p-type doped layer 115 formed on top of p+ layer 102. Photons 90 that enter p-type doped layer 115 generate carriers that are collected in the potential well of the photodiode formed in region 108 at the front surface of substrate 101. The front (upper) surface of epitaxial p-type doped layer 115 is covered by oxide layer 109 that isolates doped poly-silicon charge transfer (TX) gate 110 from substrate 101. Transfer gate 110 includes masking oxide 111 deposited on an upper surface of transfer gate 110 that serves as a patterning hard mask as well as an additional blocking mask for ion implantation that forms the photodiode storage region.
The photodiode is formed by the p+ type doped potential pinning layer 107 and n-type doped layer 108 at the front surface of substrate 101. P+ type doped layer 107 reduces dark current generated by the interface states. Charge generated by impinging photons 90 is accumulated at region 108. Gate 110 includes sidewall spacers 116 formed on each side of gate 110 to control the mutual edge positions of p+ type doped layer 107 and charge storage layer 108. Floating diffusion (FD) diode 104 formed at the front surface of substrate 101 senses charge transferred from region 108 (i.e., as shown by arrow 121, charge is transferred from region 108 at the front side of pixel substrate 101 to region 104 at the front side of pixel substrate 101). Floating diffusion 104 is connected to a source follower (SF) transistor (not shown). The floating diffusion diode, source follower, and other pixel circuit components are built within p-type doped well 103.
The pixels are isolated from each other by p+ type doped regions 105 and 106 that may extend through epitaxial p-type doped layer 115 down to p+ type doped layer 102. The pixel is covered by inter-level (IL) oxide layers 112 (only one inter-level oxide layer is shown) that are used for the pixel metal wiring and interconnect isolation. The active pixel circuit components are connected to the wiring by metal via 114 deposited through contact holes 113.
As shown in drawing 100, a large portion of valuable pixel area is occupied by transfer gate 110. Other pixel circuit components (not shown) also occupy a large portion of the pixel, so there is not enough substrate area left for the photodiode that is disposed in a lateral direction from gate 110. This can lead to low photodiode charge storage capacity, poor pixel dynamic range, and poor noise performance.
These problems are amplified when pixel 100 is operated in a global shutter mode. To operate conventional pixel 100 in global shutter mode, an additional pinned diode and an additional transfer gate are typically formed at the front surface of substrate 101 adjacent to the photodiode formed by layers 107 and 108, as can be found in Yasutomi et al. (ISSCC Digest of Technical Papers, Feb. 10, 2010, pp. 398 and 399, entitled "A 2.7e Temporal Noise 99.7% Shutter Efficiency 92 dB Dynamic Range CMOS Image Sensor with Dual Global Shutter Pixels"). This is a modification of the well-known Interline Transfer Charge Coupled Device (CCD) concept, where charge from the pixel photodiodes is transferred first to vertical CCD registers located in the spaces between the pixels, then in parallel row-by-row to a serial register, which is then followed by a CCD transfer out to a common single charge detection node connected to an amplifier.
In conventional image sensors, kTC-noise reduction is sometimes performed using feedback capacitors formed within the pixel, as can be found in Takayanagi et al. (IEEE Workshop on Charge-Coupled Devices and Advanced Image Sensors, 2001, entitled "A Four-Transistor Capacitive Feedback Reset Active Pixel and its Reset Noise Reduction Capability"). However, when feedback is performed within the pixels, the pixel circuit components occupy an even greater portion of the pixel, which can lead to further reduction in photodiode charge storage capacity, pixel dynamic range, and noise performance.
In some cases, two pixel substrates are stacked on top of each other, with one substrate having a built in photodiode and the other substrate carrying the rest of the pixel circuits. An example of two substrate stacked pixel a can be found in http://www.sony.net/SonyInfo/News/Press/201201/12-009E/ by Sony. However, when stacking the two substrates, the substrates must be electrically connected using wafer-to-wafer contacts and must be precisely aligned, resulting in increased fabrication difficulty and high manufacturing costs.
It would therefore be desirable to be able to provide improved image sensors without a stacking requirement.

Back side illuminated global shutter image sensors with back side charge storage

Semiconductor Components Industries, LLC


Certain aspects of an apparatus and a method for controlling a user interface of a device may comprise one or more sensors coupled to a vibratory surface associated with the apparatus. The one or more sensors may detect one or more vibrations of the vibratory surface caused by an interaction of an object with the vibratory surface. The one or more sensors may generate one or more vibratory signals in response to the detected one or more vibrations. One or more processors that are communicatively coupled to the one or more sensors may generate a control signal corresponding to the one or more generated vibratory signals to control the user interface of the device.

A user interface enables users to interact with devices. The user interface may be an input mechanism that enables a user to provide input to the device. The user interface may also act as an output mechanism that allows the device to indicate results of the user input. Examples of the user interface may be a button, a touch screen, a voice based user interface, a display screen, and the like. Generally, a user interface of a device may be integrated with the device or may be implemented on another device communicatively coupled to the device. Moreover, a user interface implemented using a certain technology may restrict the ways in which a user may interact with a device.
Further limitations and disadvantages of conventional and traditional approaches will become apparent to one of skill in the art, through comparison of such systems with some aspects of the present disclosure as set forth in the remainder of the present application with reference to the drawings.

Apparatus and method for controlling a user interface of a device based on vibratory signals


A system and method for automatically controlling systems and devices in a local environment, such as a home. The system comprises a control unit that receives images associated with one or more regions of the local environment. The one or more regions are each serviced by one or more servicing components. The control unit processes the images to identify, from a group of known persons associated with the local environment, any one or more known persons located in the regions. For the regions in which one or more known person is identified, the control unit automatically generates a control signal for at least one of the servicing components associated with the region, the control signal reflecting a preference of at least one of the known persons located in the respective region.

Certain home automation systems and techniques are known. Many known home automation systems and techniques may generally be classified as reactive to a real-time physical input. A well-known example are lights having attendant IR sensors (or like motion sensor), which will turn on when a person walks by, such as into a room. Such lights can often have an attendant daylight sensor (another real-time input), which will prevent the light from turning on when there is ambient daylight.
Other known home automation systems and techniques may generally be classified as pre-programmed to carry out certain functions when certain criteria are met. Many reactive systems are controlled by timers. For example, heating systems can be initiated automatically at a certain time of day, such as in the morning. Similarly, coffee makers can be automatically initiated at a specified time, so that a person has a cup of brewed coffee ready when he or she walks into the kitchen in the morning.
An example of a more complex home automation system is described in European Patent Application EP 1 102 500 A2 of Richton. The position of a wireless mobile unit (such as a wireless phone) carried by a person is used to determine the distance of the person to the home. Messages or instructions to perform certain actions based on the distance between the person and the home are generated and sent to a controller within the home. The controller causes the instruction to be enacted. For example, when the user is within a certain distance of the home, the home heating system may be instructed to turn on. Richton thus has features that are analogous to both a reactive system (i.e., a feature is engaged based upon proximity) and a pre-programmed system (i.e., engagement of a feature when certain pre-stored criteria are met).
Another example of a more elaborate pre-programmed type home automation system is described in PCT WO 01/52478 A2 of Sharood et al. In the Sharood system, existing home appliances and systems are connected to a control server. The user may control a selected appliance or system via a user interface that interacts with the server and can present graphic representations of the actual control inputs for the selected appliance or system. The user may therefore access the server and control appliances or systems remotely, for example, through an internet connection. In addition, the control server may be programmed so that certain appliances or systems are initiated and run under certain circumstances. For example, when a "vacation mode" is engaged, the lights are turned on at certain times for security purposes, and the heat is run at a lower temperature.
There are numerous deficiencies associated with the known home automation techniques and systems. For example, known reactive-type systems simply provide a fixed response when an input is received. Thus, for example, a motion sensor will switch on a light even if person would not otherwise want it on. Even a reactive system such as Richton, where certain reactions may be programmed, suffer from such a disadvantage. For example, a mobile phone that initiates certain functions in the home at certain distances that reflect a wife's preferences may create conditions that are not agreeable to a husband who is carrying his wife's phone.
Similarly, known pre-programmed type home automation systems have numerous deficiencies. For example, a timer that automatically turns on an appliance or system will do so unless it is turned off, thus creating situations that are undesirable or possibly unsafe. For example, if a person forgets to turn the timer of a coffee maker off on the day he or she has an early business meeting, a potential hazard may occur when the coffee maker is turned on later in the morning and remains on for the entire day. Likewise, for example, if the "vacation mode" is selected in Richton and a son or daughter who is unfamiliar with the system controls unexpectedly returns home from college for a weekend while the rest of the family is away, he or she may not be able to operate the lights, heating, etc. to their liking.
Other disadvantages of known home automation systems and techniques include an inability to identify a particular person and tailor a setting or response in the house to the preferences of the identified person. In addition, known systems and techniques do not respond with the preferred settings or responses based on the location of a particular person in the home. In addition, known systems and techniques do not respond with the preferred settings or responses of a number of persons based upon where they are located in the house.

System and method for adapting the ambience of a local environment according to the location and personal preferences of people in the local environment


Software and computer processor implemented system and method of providing customized automated responses to different types of incoming electronic messages from various contact sources, particularly useful for preventing distracted driving or distractions at a place of work or at a place of rest and relaxation. Here the invention's software, often in the form of an app, runs on a smartphone or other computerized device configured to automatically connect to various devices, such as automobile associated Bluetooth peripherals or WiFi access points/routers. When operating, the app causes active connections to automatically trigger auto response mode in response to incoming messages. Optionally, different automated responses to be assigned to different connected device identification codes or different incoming message originators. Various prioritization schemes, such as last active connection dominates, and various ways in which different contact specific automated responses may interact with various device specific automated responses, are also discussed.

Field of the Invention
This invention is in the field of automated telephone, email, and SMS message response schemes for communications network connected computerized systems and devices, such as smartphones, tablets or other devices which also have an ability to connect by either wired or wireless links to one or more peripherals or networks.

This patent is subject to a terminal disclaimer.

Connection specific selection of automated response messages


While a control method is established which can maximize the lifetime of an storage battery based on a SOC capable of maximizing the lifetime of the storage battery under a temperature condition and a wind condition at an electricity generation site and on currently known ones of other operational conditions, a control system is constructed which can feedback to an actual wind power generation and storage battery system. The control system includes a wind power generation and storage battery system, an storage battery operation and deterioration data collection unit for collecting data of the wind power generation and storage battery system, an storage battery operation and deterioration relation assessment unit for assessing a relation between an operation of the storage battery and deterioration thereof based on the collected data, an storage battery operation planning unit for planning such a method of operating the storage battery as to satisfy a necessary lifetime requirement using information obtained by the storage battery operation and deterioration relation assessment unit, and an storage battery operation instruction unit for instructing the wind power generation and storage battery system to operate the storage battery in accordance with the plan of the storage battery operation planning unit.

Global warming is a serious problem to all human beings and, in each of the countries in the world, to retard and stop the progress of global warming, energy saving, the use of new energy which does not emit CO2, and the like have been promoted.
In Japan also, to reduce CO2 emissions, the government determines the goal of new energy introduction, and promotes the introduction of electricity generation using new energy such as solar power, wind power, or the like, while also giving subsidy or the like.
Wind power generation using natural energy has the advantage of no emission of CO2, but an electricity output generated thereby is not stable, resulting in concerns about adverse effect on an electric power system and the deterioration of electric power quality. For the purpose of preventing such an adverse effect on an electric power system, when wind power generation is introduced, it is widely performed to simultaneously introduce an storage battery system.
FIG. 18 shows an example of an storage battery system for controlling output fluctuations in a wind power generation system. An electricity output generated by wind power generation significantly varies depending on wind conditions. If allowed to flow without any alteration, the generated electricity output exerts an adverse effect on the electric power quality of an electric power system. To prevent this, with an storage battery system using an storage battery such as a lead acid storage battery, a lithium ion battery, a super capacitor, or the like, an storage battery system output in accordance with the state of a wind power generated electricity output is produced. As a result, a wind power generated electricity output and the storage battery system output are combined to allow a smoothed system output to flow to the electric power system, and enable avoidance of the adverse effect on the electric power quality.
FIG. 19 shows an example of a requirement of interconnected system of wind power generation in an electric power company. In the example of the drawing, fluctuations in an combined output of wind power generation and the storage battery are restricted such that the difference between the maximum and minimum values of a 1-minute averaged value in 20 minutes is suppressed to be not more than 10% of a rated output of wind power, and it is requested to satisfy such a requirement of interconnected system.
It is known that the lifetime of an storage battery greatly differs depending on an operational condition. Using an storage battery for suppressing fluctuations in an output of wind power generation is a relatively new attempt. Therefore, at present, it is not entirely clear how a controllable one of operational conditions for the storage battery should be used for the operation thereof to be able to maximize the lifetime of the storage battery, while satisfying the requirement of system integration of wind power generation. Unlike in an application of conventional industrial load leveling (electric power is accumulated at night, and discharged during daytime when a load is large), in a wind power generation storage battery system, it is assumed that short-time charging and discharging are repeated in a PSOC (Parcial State of Charge) that is not a full-charged state. Even under such an unprecedented operational condition, an operation is needed which suppresses the deterioration of the storage battery, and increases the lifetime thereof to a level equal to or longer than the life cycle of a wind power generator.
Concerning a control method of the state of charge (SOC) of a lead acid storage battery, Patent Document 1 is laid open. This method is for measuring the number of times that falls within the lower limit range of SOC upon charging/discharging of the lead acid storage battery, and raising a SOC level in accordance therewith.
Concerning the maintenance of storage battery equipment, Patent Document 2 is laid open. It is disclosed therein that, when the maintenance of the storage battery equipment is performed, the capacity of each of storage batterys is checked through short-time discharging and, by replacing only the storage battery with capacity shortage, cost for storage battery replacement is reduced.

System for control of wind power generation storage battery and method of control thereof


The spring includes a composite elastomeric body having in one embodiment a closed end and an open end. A coil spring is embedded both within the body wall and the closed end, and provides reinforcement of both the body wall and the closed end. The body may be of cylindrical, conical, or other shape, depending upon the required function of the spring. It may also take an essentially hourglass shape or the shape of a cylinder flanged at both ends. Alternately, the spring may be internally pressurized to provide load leveling or air spring effects in addition to the variable rate load versus deflection curve normally obtained. The body may be attached directly to any surface to create an airtight seal. Alternately, a closure plate may be provided to seal an open end of the coil spring.

1. Field of the Invention
This invention relates to composite elastomeric springs and, more particularly, to hollow composite elastomeric springs capable of providing a variable rate spring load versus deflection curve under certain load conditions.
2. Description of the Related Art
There are many applications in which it is desirable to obtain a variable rate load versus deflection curve at or above certain load levels or deflections. Elastomeric springs often are selected for such applications, because many elastomeric materials and particularly natural rubber provide this kind of spring curve when subjected to uniaxial compression. In addition to providing variable rate spring curves, they also provide inherent vibration damping. Elastomeric springs typically take the form of solid blocks of elastomer or natural rubber.
When formed into hollow or cylindrical shapes and sealed with respect to external pressure, elastomeric springs may yield additional spring properties due to the compression of the air space within the hollow elastomeric body. For example, hollow elastomeric springs may provide spring properties generally similar to air springs while pressurized internally, or they may provide shock or load damping when selectively collapsible in response to the discharge of internal air pressure through a restricted orifice or the like. The spring effects thus obtained provide additional flexibility with respect to the variable rate spring curve obtained.
Hollow elastomeric springs, however, tend to be unstable, especially when formed with thin walls. To overcome this, some springs of this construction include a helical coil spring embedded within the wall of the elastomeric spring body. The composite elastomeric spring thus obtained is of generally tubular construction with opposed open ends. To pressurize this spring internally, it is necessary to establish continuous seals about both ends. Depending upon the construction of the load platens between which the spring is compressed, the seals tend to leak or break down both as the ends of the spring are deflected under load and as the spring resumes its relaxed state after compression.

Composite elastomeric air spring and sealing structure


In one embodiment, a processor includes multiple cores and a power control unit (PCU) coupled to the cores. The PCU has a stress detector to receive a voltage and a temperature at which the processor is operating and can calculate an effective reliability stress, maintain the effective reliability stress over multiple boot cycles of a computing system such as personal computer, server computer, tablet computer, smart phone or any other computing platform, and control one or more operating parameters of the processor based on the effective reliability stress. Other embodiments are described and claimed.

In modern processors and other semiconductor devices, it is known that as the product ages, certain degradations become manifest. Several different phenomena can cause degradation to a semiconductor device, for example, hot-carrier injection, bias temperature instability, oxide breakdown (also known as time dependent dielectric breakdown (TDDB)), electro-migration and more. Each of these degradation mechanisms occurs due to various factors like temperature, voltage, current and others. For example, a frequency degradation occurs over a product's lifetime due to negative bias temperature instability (NBTI) degradation. This degradation becomes a reliability issue for p-channel metal oxide semiconductor (PMOS) and n-channel metal oxide semiconductor (NMOS) transistors. NBTI manifests itself as an increase in the threshold voltage and consequent decrease in drain current and transconductance. The degradation is caused by temperature and voltage applied to the product over time, where the temperature and voltage impact the degradation exponentially.
One manner of handling this issue is by applying a voltage/frequency guard band at a product's beginning of life (when the product is non-aged). However, this guard band limits performance for much of the useful life of the device. For example, maximum frequency (Fmax) and minimum voltage (Vmin) settings at a beginning of life (when the product is fresh) are set assuming end of life degradation (when the product is aged). As a result, there is a speed guard band as the frequency is set lower than a maximum rated frequency of the unit at a fixed voltage and/or the voltage is set higher than a minimum rated voltage of the unit at a fixed frequency.

Determining an effective stress level on a processor


A reverse battery protection circuit for an actuator or the like. The circuit includes at least a first transistor and a second transistor which is coupled to both the first transistor and a voltage supply in a manner wherein the second transistor is adapted to turn the first transistor off in the event of an interruption in the voltage supply.

Reverse battery protection is a critical part of the automotive circuitry and electronics which must be protected from, for example, the accidental connection of the vehicle battery in the wrong polarity, as this would destroy most semiconductor chips used in the vehicle including, for example, the chips used in actuators.
Reverse battery protection in low current application circuits generally involves the use of a diode which allows current to flow in only one direction. The use of a diode has the benefit of not only protecting a circuit from an accidental reversal of battery polarity but also has the benefit of preventing a circuit's storage capacitor(s) from being discharged during battery dropouts or other common disturbances on the power supply. A disadvantage associated with the use of diodes, however, is the resultant drop in voltage (approximately 0.6V) which occurs across the diode. While this drop in voltage is insignificant in low current applications, it becomes problematic in high current applications where a large power drop across a diode can lead to overheating. This of course can be a significant issue in, for example, high temperature applications where the circuit semiconductors are already operating close to their maximum allowable junction temperatures.
Metal-oxide-semiconductor field-effect transistors (MOSFETs) have also been used in circuits for reverse battery protection. While the use of a MOSFET overcomes the issue of overheating, MOSFETs are not capable of providing any directional current flow control in the event of, for example, a very rapid discharge of a circuit's storage capacitors during, for example, dropouts or other disturbances to the power supply. In many high temperature applications, low voltage drop (and power dissipation) of the MOSFET coupled with the unidirectional flow control of the diode are both desired features.
The present invention is directed to a reverse battery circuit operable at high temperatures and tolerant of load dump pulses in excess of 200V.

Reverse battery cutoff circuit for an actuator or the like