A composition comprising (A) a copolymer which comprises (I) repeating units which are derived from a monomer having a fluoroalkyl group, a carbon-carbon double bond, (II) optional repeating units which are derived from a monomer having at least two urethane or urea bonds and a carbon-carbon double bond, but no fluorine atom, (III) optional repeating units which are derived from a monomer, the homopolymer of which having a glass transition temperature (Tg) of 50xc2x0 C. or less, (IV) optional repeating units which are derived from a monomer having a hydrophilic group and a carbon-carbon double bond, and (V) optional repeating units which are derived from a monomer having a chlorine atom and a carbon-carbon double bond; and (B) a film-forming auxiliary can impart high water and oil repellency by drying at room temperature (0 to 30xc2x0 C.) without requiring a heat treatment step.

The present invention relates to a novel composition, a water and oil repellent and a water and oil repellent product.
A conventional water and oil repellent required a heat treatment at 100xc2x0 C. or more as an essential step to impart high water and oil repellency, but various water and oil repellents have been proposed to improve processability of the water and oil repellents.
Japanese Patent Kokoku Publication No. 67511/1988 discloses a polymer obtained by binding a branch segment having a blocked fluoroalkyl group to a trunk segment of a diene copolymer, and Japanese Patent Kokai Publication No.71977/1983 discloses that a copolymer comprising a monomer having a fluoroalkyl group and a cross-linking monomer as an essential component is a water and oil repellent which imparts high water and oil repellency in a heat treatment step at low temperature. However, when both of them are dried at room temperature, the water and oil repellency is insufficient.
Furthermore, U.S. Pat. No. 5,350,795 discloses that a composition comprising fluoroacrylate/polyalkyleneglycol (meth)acrylate/polyalkyleneglycol di(meth)acrylate copolymer and Rf-containing polyalkoxypolyurethane is a water and oil repellent which imparts high water and oil repellency when it is dried at room temperature. However the water repellency is insufficient.
A conventional water and oil repellent requires a heat treatment as an essential step to impart high water and oil repellency, and sufficient water and oil repellency could not be imparted without a heat treatment.
An object of the present invention is to provide a composition which imparts high water and oil repellency only by drying at room temperature (0 to 30xc2x0 C.) without requiring a heat treatment step.
Another object of the present invention is to provide a water and oil repellent product or article comprising said composition.
The present invention provides a composition comprising
(A) a binary or more copolymer which comprises
(1) repeating units which impart water and oil repellency,
(2) repeating units which impart a solubility in a firm-forming auxiliary,
(3) optional repeating units which lower the glass transition temperature of the polymer, and
(4) optional repeating units which impart an affinity with a substrate, and
(B) a film-forming auxiliary consisting of an organic solvent which dissolves or swells the copolymer.
Repeating units (1) which impart water and oil repellency may be (I) repeating units which are derived from a monomer having a fluoroalkyl group, a carbon-carbon double bond, and optionally a urethane or urea bond.
Repeating units (2) which impart solubility in (or compatibility with) a film-forming auxiliary may be (II) repeating units which are derived from a monomer having a urethane or urea bond and a carbon-carbon double bond, but no fluorine atom; or (III) repeating units which are derived from a monomer having a carbon-carbon double bond, the homopolymer of said monomer having a glass transition temperature (Tg) of at most 50xc2x0 C.
Repeating units (3) which lower the glass transition temperature of the polymer may be (III) repeating units which are derived from a monomer having a carbon-carbon double bond, the homopolymer of said monomer having a glass transition temperature (Tg) of at most 50xc2x0 C.
Repeating units (4) which impart an affinity with a substrate may be (IV) repeating units which are derived from a monomer having a hydrophilic group and a carbon-carbon double bond, or (V) repeating units which are derived from a monomer having a chlorine atom and a carbon-carbon double bond.
The present invention provides a composition comprising
(A) a copolymer which comprises
(I) repeating units which are derived from a monomer having a fluoroalkyl group, a carbon-carbon double bond, and optionally a urethane or urea bond,
(II) optional repeating units which are derived from a monomer having a urethane or urea bond and a carbon-carbon double bond, but no fluorine atom,
(III) optional repeating units which are derived from a monomer having a carbon-carbon double bond, the homopolymer of said monomer having a glass transition temperature (Tg) of 50xc2x0 C. or less,
(IV) optional repeating units which are derived from a monomer having a hydrophilic group and a carbon-carbon double bond, and
(V) optional repeating units which are derived from a monomer having a chlorine atom and a carbon-carbon double bond and
(B) a film-forming auxiliary consisting of an organic solvent which dissolves or swells the copolymer,
wherein at least one of the repeating units (II) and the repeating units (III) is essential in the copolymer (A).
The composition of the present invention is suitable for a treatment agent, in particular a water and oil repellent.
The repeating units (I) are essential in the copolymer (A). The repeating units (II), the repeating units (III), the repeating units (IV) and the repeating units (V) are optional repeating units which have no need to be present. But at least one of the repeating units (II) and the repeating units (III) is essential.
The copolymer (A) in the composition of the present invention may be, for example:
(a) a copolymer having the repeating units (I) and (II),
(b) a copolymer having the repeating units (I) and (III),
(c) a copolymer having the repeating units (I), (II) and (III),
(d) a copolymer having the repeating units (I), (II) and (IV) and/or (V),
(e) a copolymer having the repeating units (I), (III) and (IV) and/or (V), or
(f) a copolymer having the repeating units (I), (II), (III) and (IV) and/or (V).
The present invention provides a copolymer wherein the repeating units (I), the repeating units (II) and the repeating units (III) are essential, and the repeating units (IV) and the repeating units (V) are optional.
In the repeating units (I) a fluoroalkyl group is preferably a perfluoroalkyl group.
The repeating units (I) are preferably repeating units which are derived from (meth)acrylic ester containing a fluoroalkyl group. A monomer which constitutes the repeating units (I) is preferably a compound of the formula:
Rfxe2x80x94R1xe2x80x94OCOC(R2)xe2x95x90CH2
wherein Rf is a linear or branched fluoroalkyl group having 3 to 20 carbon atoms;
R1 is a linear or branched alkylene group having 1 to 20 carbon atoms, a group of the formula: xe2x80x94SO2N(R3)R4xe2x80x94 or a group of the formula: xe2x80x94CH2CH(OR5)CH2xe2x80x94 in which R3 is an alkyl group having 1 to 10 carbon atoms, R4 is a linear or branched alkylene group having 1 to 10 carbon atoms, and R5 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms; and
R2 is a hydrogen atom or a methyl group.
Examples of the monomer (I) having a fluoroalkyl group are not limited to, but include the followings:
CF3(CF2)7(CH2)10OCOCCHxe2x95x90CH2
CF3(CF2)7(CH2)10OCOC(CH3)xe2x95x90CH2
CF3(CF2)6CH2OCOCHxe2x95x90CH2
CF3(CF2)8CH2OCOC(CH3)xe2x95x90CH2
(CF3)2CF(CF2)6(CH2)2OCOCHxe2x95x90CH2
(CF3)2CF(CF2)8(CH2)2OCOCHxe2x95x90CH2
(CF3)2CF(CF2)10(CH2)2OCOCHxe2x95x90CH2
(CF3)2CF(CF2)6(CH2)2OCOC(CH3)xe2x95x90CH2
(CF3)2CF(CF2)8(CH2)2OCOC(CH3)xe2x95x90CH2
(CF3)2CF(CF2)10(CH2)2OCOC(CH3)xe2x95x90CH2
CF3CF2(CF2)6(CH2)2OCOCHxe2x95x90CH2
CF3CF2(CF2)8(CH2)2OCOCHxe2x95x90CH2
CF3CF2(CF2)10(CH2)2OCOCHxe2x95x90CH2
CF3CF2(CF2)6(CH2)2OCOC(CH3)xe2x95x90CH2
CF3CF2(CF2)8(CH2)2OCOC(CH3)xe2x95x90CH2
CF3CF2(CF2)10(CH2)2OCOC(CH3)xe2x95x90CH2
CF3(CF2)7SO2N(CH3)(CH2)2OCOCHxe2x95x90CH2
CF3(CF2)7SO2N(C2H5)(CH2)2OCOCHxe2x95x90CH2
(CF3)2CF(CF2)8CH2CH(OCOCH3)CH2OCOC(CH3)xe2x95x90CH2
(CF3)2CF(CF2)6CH2CH(OH)CH2OCOCHxe2x95x90CH2
The monomer (I) having a urethane or urea bond and a fluoroalkyl group may be a compound of the general formula:
Rf1xe2x80x94X1xe2x80x94A1xe2x80x94CONHxe2x80x94Y1xe2x80x94NHCOxe2x80x94A2xe2x80x94Oxe2x80x94C(xe2x95x90O)xe2x80x94CR3xe2x95x90CH2
wherein Rf1 is a fluoroalkyl group having 4 to 16 carbon atoms;
X1 is xe2x80x94R1xe2x80x94, xe2x80x94CON(R2)xe2x80x94Q1xe2x80x94 or xe2x80x94SO2N(R2)xe2x80x94Q1xe2x80x94, in which R1 is an alkylene group, R2 is a hydrogen atom or a lower alkyl group and Q1 is an alkylene group;
A1 is xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94N(R2)xe2x80x94, in which R2 is a hydrogen atom or a lower alkyl group;
Y1 is a residue remaining by removing an isocyanate from an aromatic or alicyclic diisocyanate;
A2 is a bivalent organic group having 2 to 9 carbon atoms and capable of containing at least one oxygen atom; and
R3 is a hydrogen atom or a methyl group.
Specific examples of the monomer (I) having a urethane or urea bond and a fluoroalkyl group are as follows:
A monomer having a urethane or urea bond and a fluoroalkyl group, which constitutes the repeating units (I), may be a monomer obtained by reacting
(I-a) a compound having at least two isocyanate groups,
(I-b) a compound having one carbon-carbon double bond and at least one hydroxyl or amino group, and
(I-c) a compound having a fluoroalkyl group and one hydroxyl or amino group; or
a monomer obtained by reacting a compound having one isocyanate group and at least one carbon-carbon double bond with the compound (I-c).
The monomer (II) having a urethane or urea bond and a carbon-carbon double bond, but no fluorine atom may be a monomer obtained by reacting
(II-a) a compound having at least two isocyanate groups, and
(II-b) a compound having one carbon-carbon double bond and at least one hydroxyl or amino group with (II-c-1) a compound having at least one hydroxyl or amino group, and a polyoxyalkylene chain or a polysiloxane chain, or
(II-c-2) a compound having at least one hydroxyl or amino group; or
a monomer obtained by reacting a compound having one isocyanate group and at least one carbon-carbon double bond with the compound (II-c-1) or (II-c-2).
Examples of the compound (II-a) are as follows:
The compound (II-a) is preferably diisocyanate. But triisocyanate and polyisocyanate can be also used for the reaction.
For example, a trimer of diisocyanate, polymeric MDI (diphenylmethanediisocyanate) as well as an adduct of polyhydric alcohols such as trimethylol propane, trimethylol ethane and glycerin to a diisocyanate can be also used in the reaction.
Examples of triisocyanate and polyisocyanate are as follows:
The compound (II-b) may be, for example, a compound of the formula:
wherein R1 is a hydrogen atom or a methyl group, p is a number of 1 to 300 (e.g. 1 to 20) and X is as follows:
wherein p, m and n are a number of 1 to 300, respectively.
The compound (II-c-1) may be a compound of the formula:
R1xe2x80x94(Oxe2x80x94R2)nxe2x80x94OH
R1xe2x80x94(Oxe2x80x94R2)nxe2x80x94NH2

wherein R1 represents a hydrogen atom or a C1 to C22 alkyl group, in the latter case a hetero atom, or an aromatic or an alicyclic compound may be contained; R2 represents a linear or branched C1 to C6 alkylene group; R3 and R4 represents a hydrogen atom or a C1 to C6 alkyl group which optionally contains a hetero atom, or an aromatic or an alicyclic compound, or optionally contains a modification such as fluorine modification, polyether modification, alcohol modification, amino modification, epoxy modification, epoxy ether modification, phenol modification, carboxyl modification, and mercapto modification; and n represents an integer of 1 to 50. Preferred R1, R3 and R4 groups are CH3 and preferred R2 group is C2H4 and C3H6.
Examples of the compound (II-c-1) are polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, end silanol group dimethyl silicone and end amino-modified dimethyl silicone.
The compound (II-c-2) has neither of a polyoxyalkylene chain nor a polysiloxane chain. The compound (II-c-2) may be a compound of the formula:
R2xe2x80x94OH
R2xe2x80x94NH2 or
R2xe2x80x94NHxe2x80x94R3
wherein R2 and R3, the same or different, represent a C1 to C22 alkyl group and optionally contain a hetero atom, or an aromatic or an alicyclic compound. Preferred R2 and R3 groups are C8H17, C18H37, C4H9 and cyclohexyl.
Examples of the compound (II-c-2) include butyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, stearyl alcohol, oleyl alcohol, benzyl alcohol, cyclohexyl alcohol, 2-ethylhexylamine and stearylamine.
The compound (II-a), (II-b) and (II-c-1) or (II-c-2) are reacted in amounts of, when (II-a) is diisocyanate, one mol of (II-b) and (II-c-1) or (II-c-2) per one mol of (II-a), and when (II-a) is triisocyanate, one mol of (II-b) and two mols of (II-c-1) or (II-c-2) per one mol of (II-a).
A monomer which constitutes the repeating units (III) may be a monomer having conjugated double bonds or one or two carbon-carbon double bonds, and a glass transition temperature (Tg) of 50xc2x0 C. or less, for example 30xc2x0 C. or less, particularly 0xc2x0 C. or less.
The term xe2x80x9ca monomer having a glass transition temperature (Tg) of 50xc2x0 C. or lessxe2x80x9d means that the homopolymer consisting of said monomer has a glass transition temperature (Tg) of 50xc2x0 C. or less. Tg was measured by using DSC, Model 7 manufactured by Perkin Elmer Co.
A monomer which constitutes the repeating units (III) is preferably a diene monomer, a (meth)acrylic ester monomer or a di(meth)acrylic ester monomer.
The (meth)acrylic ester monomer may be a compound of the general formula:
CH2xe2x95x90CA1COOA2
or
CH2xe2x95x90CA1COO(R1xe2x80x94O)nxe2x80x94A2
wherein A1 is a hydrogen atom or a methyl group,
A2 is a linear or branched C1 to C30 alkyl group,
R1 is a linear or branched C1 to C6 alkylene group and
n is an integer of 1 to 30.
The di(meth)acrylic ester monomer may be a compound of the general formula:
CH2xe2x95x90CA1COO(R1)nOOCA1Cxe2x95x90CH2
or
xe2x80x83CH2xe2x95x90CA1COO(R1xe2x80x94O)nxe2x80x94OCA1Cxe2x95x90CH2
wherein A1 is a hydrogen atom or a methyl group,
R1 is a linear or branched C1 to C6 alkylene group, and
n is an integer of 1 to 30.
Examples of the monomer having a glass transition temperature of 30 to 50xc2x0 C. include cetyl acrylate and isobutyl methacrylate for examples of the (meth)acrylic ester monomer; and polyethylene glycol(4)diacrylate for examples of the di(meth)acrylic ester monomer.
Examples of the monomer having a glass transition temperature of 0 to 30xc2x0 C. include methyl acrylate, n-butyl methacrylate, and cetyl methacrylate for examples of the (meth)acrylic ester monomer.
Examples of the monomer having a glass transition temperature of 0xc2x0 C. or less include isoprene and 1,3-butadiene for examples of the diene monomer; and ethyl acrylate, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate for examples of the (meth)acrylic ester monomer.
A monomer which constitutes the repeating units (IV) and has a hydrophilic group and a carbon-carbon double bond may be, for example a compound of the formula:
CH2xe2x95x90CA1xe2x80x94C(xe2x95x90O)xe2x80x94X1xe2x80x94A2
wherein A1 is a hydrogen atom or a methyl group,
X1 is xe2x80x94Oxe2x80x94, xe2x80x94CH2xe2x80x94 or xe2x80x94NHxe2x80x94,
A2 is a hydrogen atom, a hydrophilic group or a group containing a hydrophilic group.
Examples of the hydrophilic group include a hydroxyl group, a glycidyl group, an ester group, an amine group, a urethane group, a phosphate group, a sulfate group and the like.
Examples of the monomer which constitutes the repeating units (IV) include glycidyl methacrylate, hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxyethyl acrylate, glycerol monomethacrylate, xcex2-acryloyloxyethyl hydrogen succinate, xcex2-methacryloyloxyethyl hydrogen phthalate, 2-acryloyloxyethylhexahydrophthalic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, hydroxypropyl methacrylate trimethylammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-acryloyloxyethyl acid phosphate, glucosylethyl methacrylate, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-methacryloyloxyethyl acid phosphate and neopentyl glycol hydroxypivalate diacrylate.
A monomer which constitutes the repeating units (V) and has a chlorine atom and a carbon-carbon double bond may be, for example, a compound of the formula:
CY1Y2xe2x95x90CY3xe2x80x94Z
wherein Y1 and Y2 is respectively a hydrogen atom or a fluorine atom,
Y3 is a hydrogen atom, a fluorine atom, a chlorine atom or a methyl group,
Z is a chlorine atom or a chlorine atom-containing group.
Examples of the chlorine-containing monomer which constitutes the repeating units (V) include vinyl chloride, vinylidene chloride, 3-chloro-2-hydroxypropyl methacrylate and monochlorotrifluoroethylene.
A weight average molecular weight of the copolymer (A) is preferably from 2,000 to 1,000,000.
The amount of the repeating units (I) is preferably from 40 to 90% by weight,
and more preferably from 50 to 80% by weight,
the amount of the repeating units (II) is 60% by weight or less, e.g. from 5 to 60% by weight, and more preferably from 10 to 50% by weight,
the amount of the repeating units (III) is 60% by weight or less, e.g. from 1 to 60% by weight, and more preferably from 1 to 50% by weight,
the amount of the repeating units (IV) is 30% by weight or less, and more preferably from 0.1 to 20% by weight, and
the amount of the repeating units (V) is 30% by weight or less, and more preferably from 0.1 to 20% by weight,
based on the amount of the copolymer (A).
The film-forming auxiliary (B) which facilitates the film-forming of the copolymer (A) by existing together with the copolymer (A) is preferably those which dissolves, swells or softens the copolymer (A).
The film-forming auxiliary (B) may be (i) an alcohol, glycol ether, ketone, ether and ester having a C1 to C22 alkyl chain, or (ii) a linear or cyclic silicone.
The film-forming auxiliary (B) (i) may be a compound containing a fluorine atom, a hetero atom, an aromatic ring or an aliphatic ring.
The film-forming auxiliary (B) (ii) may be a compound of the formula:
wherein R9 and R10 each represents a hydrogen atom or a C1 to C6 alkyl group, which optionally contains a hetero atom, an aromatic or an alicyclic compound, or optionally contains a modification such as fluorine modification, polyether modification, alcohol modification, amino modification, epoxy modification, epoxy ether modification, phenol modification, carboxyl modification and mercapto modification; and n represents a number of 1 to 50.
As the film-forming auxiliary (B), a compound having the value of the solubility parameter (sp) at 25xc2x0 C. of 5 to 15, e.g. 8 to 11 is suitable. The solubility parameter is calculated according to Fedors"" method (R. F. Fedors, Polym. Eng. Sci., 14(2), 147(1974)).
The role of the film-forming auxiliary is to dissolve, swell or soften the copolymer (A) and induce film-formation of the copolymer (A) with a low calorie. This makes it possible to impart high water and oil repellency without requiring any heat treatment step. The film-forming auxiliary may be single compound or two or more of them may be used in combination. The film-forming auxiliary may be the same as or different from the polymerization solvent.
Examples of the film-forming auxiliary (B) include, for example, ethanol, dipropylene glycol monomethyl ether, 1-methoxy-2-propanol, diethylene glycol acetate monoethyl ether, di-n-butyl adipate, butyl carbitol acetate, octamethyltrisiloxane and decamethylcyclopentasiloxane.
The composition of the present invention may comprise 30 to 99.9 parts by weight, particularly 40 to 95 parts by weight, e.g. 50 to 80 parts by weight of the copolymer (A) and 0.1 to 70 parts by weight, particularly 5 to 60 parts by weight, e.g. 20 to 50 parts by weight of the film-forming auxiliary (B).
The copolymer can be prepared by emulsion polymerization, solution polymerization or suspension polymerization. In particular, the emulsion polymerization is preferred.
The copolymer of the present invention can also be produced in an aqueous emulsion. Monomers are emulsion-polymerized by use of water, an emulsifying agent and optionally an organic solvent. The film-forming auxiliary (B) may be added before or after the emulsion polymerization. The mixture may previously be emulsified by a high-pressure emulsifying machine or the like before polymerization.
The emulsifying agent used may be any type of a surface active agent, such as an anionic, cationic or nonionic surface active agent.
Examples of the anionic surface active agent include sodium lauryl sulfate, lauryl sulfate triethanolamine, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonyl phenyl ether sulfate, polyoxyethylene lauryl ether sulfate triethanolamine, sodium cocoyl sarcosine, sodium N-cocoyl methyl taurine, sodium polyoxyethylene coconut alkyl ether sulfate, sodium diether hexyl sulfosuccinate, sodium xcex1-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, and perfluoroalkyl carboxylate salt (Unidine DS-101 and 102 manufactured by Daikin Industries Ltd.).
Examples of the cationic surface active agent include dialkyl (C12-C22) dimethyl ammonium chloride, alkyl (coconut) dimethyl benzyl ammonium chloride, octadecyl amine acetate salt, tetradecyl amine acetate salt, tallow alkyl propylene diamine acetate salt, octadecyl trimethyl ammonium chloride, alkyl (tallow) trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, alkyl (coconut) trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, alkyl (tallow) imidazoline quaternary salt, tetradecyl methyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, dioleyl dimethyl ammonium chloride, polyoxyethylene dodecyl monomethyl ammonium chloride, polyoxyethylene alkyl (C12-C22) benzyl ammonium chloride, polyoxyethylene lauryl monomethyl ammonium chloride, 1-hydroxyethyl-2-alkyl (tallow) imidazoline quaternary salt, a silicone-based cationic surface active agent having a siloxane group as a hydrophobic group, and a fluorine-based cationic surface active agent having a fluoroalkyl group as a hydrophobic group (Unidine DS-202 manufactured by Daikin Industries Ltd.).
Examples of the nonionic surface active agent include polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene mono-oleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monostearate, sorbitan mono-oleate, sorbitan sesqui-oleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan mono-oleate, polyoxyethylene polyoxypropylene block polymer, polyglycerin fatty acid ester, polyether-modified silicone oil (SH3746, SH3748, SH3749 and SH3771 manufactured by Toray Dow Corning Silicone Co., Ltd.), perfluoroalkyl ethylene oxide adduct (Unidine DS-401 and DS-403 manufactured by Daikin Industries Ltd.), fluoroalkyl ethylene oxide adduct (Unidine DS-406 manufactured by Daikin Industries Ltd.), and perfluoroalkyl oligomer (Unidine DS-451 manufactured by Daikin Industries Ltd.).
Examples of the organic solvent used in the emulsion polymerization are the same as the organic solvent used in the solution polymerization described hereinafter.
The copolymer of present invention can be produced by the solution polymerization in an organic solvent. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate, butyl acetate, dibutyl adipate and dibutyl succinate; alcohols such as ethanol, isopropanol, butanol, 1,3-butanediol and 1,5-pentanediol; halogenated hydrocarbon such as perchlorethylene, trichlene, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,2,2,3,3,3-pentafluoropropane and 1,1-dichloro-1-fluoroethane (HCFC-141b); hydrocarbons such as octane, petroleum, toluene and xylene; dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, polypropylene glycol, triethylene glycol dimethyl ether, propylene glycol and ethylene glycol.
The preferred organic solvents are ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate, 1,1-dichloro-1-fluoroethane and the like.
In polymerization, a polymerization initiator, an ionizing radiation such as xcex3-ray and the like is used to initiate the polymerization. Examples of the polymerization initiator are an organic peroxide, an azo compound, a persulfate salt and the like.
Examples of the organic peroxide include t-butyl peroxy pivalate, benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide and diisopropyl peroxy dicarbonate. Examples of the azo compound include 2,2xe2x80x2-azobisisobutyronitrile, 2,2xe2x80x2-azobis(2-amidinopropane)dihydrochloride, 2,2xe2x80x2-azobis(2-methyl butaneamidooxime)dihydro-chloride and 2,2xe2x80x2-azobis(2-methylbutyronitrile).
The copolymer of the present invention can be used as a treatment agent. The treatment agent may be a water and oil repellent. The treatment agent comprises the copolymer and the film-forming auxiliary, an optional polymerization solvent and diluting solvent. The diluting solvent may be water, an alcohol (e.g. alkanol), a ketone, an ester, an ether (e.g. a glycol ether) or a mixture of them. In particular, the diluting solvent is preferably water. The film-forming auxiliary, the diluting solvent and the polymerization solvent may be different one another. When the diluting solvent and the polymerization solvent are different each other, the polymerization solvent may be removed (by evaporation, etc.) before using the treatment agent.
The alcohol used as the diluting solvent includes C1 to C4 lower alkanols such as methanol, ethanol, 2-propanol and n-butanol. Among these lower alkanols, ethanol and 2-propanol are preferable in view of safety. Alkanols having at least five carbon atoms are not preferable because of poor drying characteristics. These lower alkanols can be used singly or in combination thereof.
Solvents such as isoparaffin, n-heptane, n-hexane, mineral terpene, ethyl acetate, toluene, methyl ethyl ketone and methyl isobutyl ketone can be added at a less dangerous level. An alternative fluorocarbon such as fluorocarbon 141b can also be used as a matter of course. Further, the addition of a small amount of glycol ethers such as dipropylene glycol monomethyl ether is also effective in preventing whitening.
A wide variety of additives can be added to the treatment agent of the present invention according to necessity. Among the additives, an organopolysiloxane is important because it can improve water repellency. The organopolysiloxane used may be a silicone oil, a silicone dispersion or a mixture thereof. The silicone oil is most typically dimethyl polysiloxane having various degrees of polymerization at a viscosity ranging from 0.65 to 300,000 cS at 25xc2x0 C., which is represented by the following formula:
Further, a main chain of some organopolysiloxanes may contain a small amount of the following group:
Other examples include those having xe2x80x94(CH3CH2)SiOxe2x80x94, xe2x80x94CH3)HSiOxe2x80x94, xe2x80x94(C6H5)2SiOxe2x80x94, xe2x80x94(C6H5)(CH3)SiOxe2x80x94 or a mixture of these groups, in place of xe2x80x94(CH3)2SiOxe2x80x94. Further, some organopolysiloxanes may have the terminal of the main chain Sixe2x80x94Oxe2x80x94Si substituted with a hydroxyl group. Further, there are a wide variety of modified silicone oil having these side chains chlorinated or being modified by introducing an amino group, epoxy group, polyether group, carboxyl group, hydroxyl group, trifluoroalkyl group, alcohol ester group, alkyl group or the like. The silicone dispersion is a dispersion in which silicone resin or silicone rubber at an initial stage of polymerization has been dissolved in a solvent, and it forms a film having a three-dimensional network structure through condensation upon heating. In the present invention, a wide variety of organopolysiloxanes can be used without limitation to those enumerated above. For these organopolysiloxanes, there are many types of commercial products. Examples of the commercial products include SH200, PRX413, SH8011 and SD8000 (manufacture by Toray Dow Corning Silicone Co., Ltd.), KP-801M, KPN-3504 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of organopolysiloxane incorporated may be from about 0.05 to about 10% by weight, preferably from about 0.5 to 5% by weight, based on the treatment agent of the present invention.
Stain preventing agents, UV absorbents, surface active agents, disinfectants, insecticides, antistatic agents, perfumes or the like as described in Japanese Patent Kokoku Publication Nos. 6163/1987 and 33797/1988 may be added to the treatment agent of the present invention according to necessity. In order to soften treated fabrics, to prevent charging of treated fabrics, to improve water and oil repellency and to improve shrink-resistance, an antistatic agent, an aminoplast resin, an acrylic polymer, a natural wax, a silicone resin or the like may further be added in such amounts that the effect of the present invention is not inhibited.
The treatment agent, in particular the water and oil repellent of the present invention may be composed of aqueous emulsion-type composition prepared by the emulsion polymerization method.
The water and oil repellent of the present invention can be applied to a substrate according to a conventionally known method. A method of dispersing said water and oil repellent into an organic solvent or water to dilute it, attaching it on the surface of the substrate by a procedure such as dip application, spray application, foam application to the substrate and the like, and drying it is usually adopted. The drying may be carried out by allowing to stand (solar drying or shade drying) at room temperature (0 to 30xc2x0 C.) or by heat-drying with a household dryer, an iron and a drier. If necessary, the curing may be also carried out by applying the water and oil repellent together with an appropriate closslinking agent. Furthermore, in addition to the water and oil repellent of the present invention, mothproofing agents, softening agents, anti-microbial agents, flame-retardants, antistatic agents, paint primers and crease-retardants can also be added and used in combination. In case of the dip application, the concentration of the copolymer in the treatment liquid may be from 0.05 to 10% by weight. In case of the spray application, the concentration of the copolymer in the treatment liquid may be from 0.1 to 5% by weight.
The water and oil repellent may be in the form of emulsion, aerosol, solid or paste.
The water and oil repellent may be used in a water and oil repellent product or article.
The water and oil repellent product may comprise, for example (a) a water and oil repellent alone, (b) a water and oil repellent and an application apparatus, or (c) a water and oil repellent and a container in which the water and oil repellent is contained.
The water and oil repellent product which comprises a water and oil repellent emulsion may be for example (i) a water and oil repellent product comprising a water and oil repellent which is charged in a container equipped with a mechanism for spraying a liquid in said container outside (for example using a trigger type container); or (ii) a water and oil repellent product comprising a water and oil repellent which is charged in a container equipped with a mechanism for propelling a liquid in said container outside using a pressure (for example using a manual pump container or an aerosol type container). It may be also a water and oil repellent product in the form of foam comprising the emulsion containing additionally a foaming agent which is charged in the container of (i) or (ii). When a water and oil repellent product in the form of foam is used, examples of the foaming agent which is added to the emulsion are preferably an anionic surfactant, a cationic surfactant, an amphoteric surfactant or a nonionic surfactant which has the foaming property previously known.
As the anionic surfactant, for example, sodium alkyl aryl sulfonate salt, sodium alkyl sulfuric ester salt, sodium alkyl sulfonate, sodium dialkyl sulfosuccinate, sodium polyoxyethylene alkyl aryl ether sulfuric ester, sodium polyoxyethylene alkyl ether sulfuric ester, sodium perfluoroalkylamido-N-propionate salt and the like are preferred.
As the cationic surfactant, alkyl aryl trimethyl ammonium chloride, alkyl trimethyl ammonium chloride and alkyl dimethyl amine acetate salt are preferred.
As the amphoteric surfactant, for example, alkylbetaine and alkylimidazoline are preferred.
As the nonionic surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkylamide, polyoxyethylene lanolin alcohol, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, dimethylalkylamine oxide, bishydroxyethyl alkylamine oxide, N-alkylmorpholine oxide, polyoxyethylene fatty acid alkylolamide and sucrose ester are preferred.
Among them, the foaming agent is preferably those which have the initial foam height of at least 30 mm at the concentration of the foaming surfactant of 0.1% by weight at 30xc2x0 C. when measuring according to the foaming measurement method of JIS K-3362.
The amount of the foaming surfactant is preferably from 0.007 to 2 parts by weight based on 100 parts by weight of the treatment agent of the present invention.
The water and oil repellent is sprayed or coated to the substrate, or the substrate is dipped into the water and oil repellent using these water and oil repellent products. When it is coated, a coating apparatus such as a sponge, a roller or a brush may be used and these coating apparatuses may be equipped in the container.
The water and oil repellent in the form of solid or paste is applied to the substrate. The water and oil repellent product which comprises the water and oil repellent in the form of solid may be charged in a stick type container such that being used for a lipstick or in a box type container such that being used for car wax. The water and oil repellent product which comprises the water and oil repellent in the form of paste may be charged in a tube type container such that being used for a dentifrice or in a box type container such that being used for car wax. When the water and oil repellent is applied, an application apparatus such as a sponge, a roller or a brush may be used and these application apparatuses may be equipped in the container.
The water and oil repellent of the present invention may be used as an aerosol. The water and oil repellent of the present invention can easily form the aerosol by adding a propellant to the stock liquid and charging in a container. As the propellant, liquid petroleum gas (LPG), propane, butane, dimethyl ether, carbon dioxide, nitrogen gas and the like can be used. Optionally, an alternative fluorocarbon such as HFC-134a and HCFC-141b is also used. The weight ratio of the stock liquid to the propellant is from 99.5/0.5 to 30/70, and preferably from 99/1 to 50/50.
A substrate to be treated with the water and oil repellent of the present invention is preferably a textile. As the textile, various examples can be recited. Examples of them include an animal- and vegetative-origin natural fiber such as cotton, hemp, wool and silk; a synthetic fiber such as a polyamide, a polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene; a semi-synthetic fiber such as rayon and acetate; an inorganic fiber such as glass fiber, carbon fiber and asbestos fiber; or a mixture of these fibers.
The textile may be any of in the form of yarn, fabric and the like. Examples of the substrate which can be treated with the water and oil repellent of the present invention include glass, paper, wood, leather, fur, asbestos, brick, cement, metal and metal oxide, ceramics (e.g. tile), plastic, coating surface and plaster, rubber, cork and the like, in addition to a textile.
Examples of the substrate to be treated include:
garments, for example, undergarment, hosiery, overgarment, trousers, coat, raincoat, hat, gloves, shoes, boots, kimono, formalwear, full dress, accessory, dress shirt, necktie, belt, slippers, fastener and clothing for pet;
interiors, for example, outer packaging of light fitment, chair, sofa, table, drawer, sideboard, wall paper, wall material, tatami (Japanese mat), floor material, screen, paper screen, window screen, glass, curtain, carpet, mat and dust-bin:
kitchen apparatus, for example, range hood, sink, counter top, exhaust fan, tablecloth, dust receiver of sink, coaster and apron;
bath and toilet article, for example, bathtub, tile, basin, bath pail, toilet bowl, paper holder and bedpan;
bedclothings, for example, bed, bed pad and futon (Japanese bedding);
domestic appliances, for example, inner and outer packaging of refrigerator, inner and outer packaging of washing machine, outer packaging of AV apparatus, outer packaging of telephone, outer packaging of air conditioner and outer packaging of cleaner;
travel and leisure goods, for example, suitcase, lingerie case, toilet goods porch and cosmetic porch;
car and bike goods, for example, glass, mirror, lamp, seat, inner lining, mat, wheel, outer packaging, inner lining of trunk and wiper;
sports and outdoor goods, for example, gloves, baseball gloves, shoes, cap, wear, helmet, racket, golf club, bat, ski boards, snow board, skating board, beach goods, goggle, tent, sleeping bag, sheet, swimsuit, wetsuit, ball, bag, rucksack and fishing tackle;
other daily use sundries, for example, umbrella, bag, purse, key, outer packaging of mobile phone, watch, eyeglasses, sunglasses, pocket date book, buisiness card, toy, book, outer packaging of game machine, pet goods, instrument, baby bogie, tricycle and bicycle; and
facility, for example, outer packaging of post and telephone box.


The invention relates to FMS-like tyrosine kinase (FLT3), FLT3 binding pockets or FLT3-like binding pockets. The invention relates to a computer comprising a data storage medium encoded with the structure coordinates of such binding pockets. The invention also relates to methods of using the structure coordinates to solve the structure of homologous proteins or protein complexes. The invention relates to methods of using the structure coordinates to screen for and design compounds that bind to FMS-like tyrosine kinase protein, complexes of FMS-like tyrosine kinase protein, homologues thereof, or FLT-3-like protein or protein complexes. The invention also relates to crystallizable compositions and crystals comprising an FMS-like tyrosine kinase cytoplasmic domain or homologues thereof. The invention also relates to methods of identifying inhibitors of the cytoplasmic domain of FMS-like tyrosine kinase protein.

The FMS-like tyrosine kinase (FLT3) is a type III receptor tyrosine kinase that is thought to play a key role in hematopoiesis. Certain classes of FLT3 mutations cause constitutively activated forms of the receptor that are found in significant numbers of patients with acute myeloid leukemia (AML). The mutations occur in either the activation loop, for example, as point mutations of Asp835, or as internal tandem duplication (ITD) sequences in the juxtamembrane (JM) domain.
FLT3 (FMS-like tyrosine kinase 3) (Gilliland, D. G., and Griffin, J. D., Blood 100: 1532-1542 (2002); D. Kottaridis, P., et. al., Br. J. Haematol. 122, 523-538 (2003); Stirewalt, D. L. and Radich, J. P. Nat. Rev. Cancer 3: 650-665 (2003)), also known as FLK-2 (fetal liver kinase 2) and STK-1 (human stem cell kinase 1), belongs to a family of type III receptor tyrosine kinases (RTKs) (Rosnet, O., et. al., Oncogene 6: 1641-1650 (1991); Rosnet, O., et. al., Genomics 9: 380-385 (1991); Small, D., et. al., Proc. Natl. Acad. Sci. USA 91, 459-463 (1994); Matthews, W., et. al., Cell 65: 1143-1152 (1991)). Members of a subset of this family include FLT3, platelet-derived growth factor receptors α and β (PDGFRα and PDGFRβ) (Yarden, Y., et. al., Nature 323: 226-232 (1986); Claesson-Welsh, L., et. al., Methods Enzymol. 198: 72-77 (1991); Claesson-Welsh, L et. al., Proc. Natl. Acad. Sci. USA 86: 4917-4921 (1989); Matsui, T., et. al., Science 243: 800-804 (1989)), FMS (Stanley, E. R., et. al., J. Cell. Biochem. 21:151-159 (1983)) and cKIT (Yarden, Y et. al., EMBO J. 6: 3341-3351 (1987); Mol, C. D., et. al., J. Biol. Chem. 278: 31461-31464 (2003)) and are characterized by an extracellular domain consisting of five immunoglobulin-like (Ig-like) domains, a single transmembrane region, a cytoplasmic juxtamembrane domain (JM) and a cytoplasmic tyrosine kinase domain interrupted by a kinase insert domain (KID) (Agnes, F., et. al., Gene 145: 283-288 (1994); Rosnet, O., and Birnbaum, D. (1993) Crit. Rev. Oncog. 4, 595-61; Scheijen, B., and Griffin, J. D. Oncogene 21: 3314-3333 (2002)). Two groups independently reported the cloning of the flt3 gene (Rosnet, O., et. al., Oncogene, supra; Rosnet, O., et. al., Genomics, supra; Matthews, W et. al., supra).
Subsequently, FL, the ligand for FLT3, and a type I transmembrane protein was cloned from mouse (Lyman, S. D., et. al., Stem Cells 12 Suppl 1: 99-107; discussion 108-110 (1994); Lyman, S. D et. al., Oncogene 11: 1165-1172 (1995); Hannum, C., et. al., Nature 368: 643-648 (1994); Savvides, S. N., et. al., Nat. Struct. Biol. 7: 486-491 (2000)). The binding of FL leads to dimerization, activation and autophosphorylation of the receptor and subsequent activation of several signaling pathways including STAT5 (Zhang, S., et. al., J. Exp. Med. 192: 719-728 (2000)), Ras/mitogen-activated protein kinase (MAPK) and phosphatidylinositol 3 kinase (PI3K)/AKT pathways. The human flt3 gene encodes a 993 amino acid protein of which residues 572-603 and 604-958 represent the JM and tyrosine kinase domains, respectively (Rosnet, O., et. al., Blood 82: 1110-1119 (1993)).
FLT3 is primarily expressed in immature hematopoietic cells (Rosnet, O., et. al., Genomics, supra; deLapeyriere, O., et. al., Differentiation 58: 351-359 (1995)) and is essential for the normal function of stem cells and the immune system (deLapeyriere, O., et. al., supra; Brasel, K., et. al., Leukemia 9: 1212-1218 (1995); Turner, A. M., et. al., Blood 88: 3383-3390 (1996)). FLT3 is also found in placenta, gonads and brain (Maroc, N., et. al., Oncogene 8: 909-918 (1993)) and is expressed in high levels in a wide range of hematopoietic malignancies including 70-100% of acute myelogenous leukemia (AML), acute lymphoblastic leukemia (ALL) and chronic myelogenous leukemia (Rosnet, O., et. al., Acta Haematol. 95: 218-223 (1996); Drexler, H. G. Leukemia 10: 588-599 (1996)).
Two distinct types of FLT3 mutations have been identified in up to 41% of AML patients. Internal tandem duplication (ITD) mutations within the JM domain contribute to about 17-34% of FLT3 activating mutations in AML (Nakao, M., et. al., Leukemia 10: 1911-1918 (1996); Thiede, C., et. al., Blood 99: 4326-4335 (2002)). FLT3-ITD has also been detected at low frequency in myelodysplastic syndrome (MDS) (Yokota, S., et. al., Leukemia 11: 1605-1609 (1997)); Horiike, S., et. al., Leukemia 11: 1442-1446 (1997)). The ITDs are always in-frame, and are limited to the JM domain. However, they vary in length and position from patient to patient. These repeat sequences may serve to disrupt the autoinhibitory activity of the JM domain resulting in the constitutive activation of FLT3. Point mutations at aspartate 835 within the activation loop of the FLT3 kinase domain represent a second class of activating mutations (Yamamoto, Y., et. al., Blood 97: 2434-2439 (2001); Abu-Duhier, F. M., et. al., Br. J. Haematol. 113: 983-988 (2001)). FLT3-Asp835 mutations also lead to constitutive activation of the receptor and have been reported in 7% of AML, 3% of MDS and 3% of all cases. The most common substitution is Asp835Tyr, but other substitutions including Asp835Val, Asp835His, Asp835Glu and Asp835Asn have also been reported (Yamamoto, Y., et. al., supra). Both FLT3-ITD and FLT3-Asp835 mutations are associated with FLT3 autophosphorylation and phosphorylation of downstream targets (Yamamoto, Y., et. al., supra; Mizuki, M., et. al., Blood 96: 3907-3914 (2000); Mizuki, M., et. al., Blood 101: 3164-3173 (2003); Hayakawa, F., et. al., Oncogene 19: 624-631 (2000)).
A novel class of constitutively activated FLT3 mutants has been recently identified in AML patients in which isoleucine 836 is either deleted (FLT3-Ile836del) or substituted with methionine and arginine (FLT3-Ile836Met+Arg) (Thiede, C., et. al., supra). In mice, injection of FLT3-ITD transformed cells results in leukemia-like syndrome (Mizuki, M., et. al., (2000), supra). Several FLT3 inhibitors, such as PKC412 (N-benzoyl staurosporine) (Fabbro, D., et. al., Anticancer Drug Des. 15: 17-28 (2000); Weisberg, E., et. al., Cancer Cell 1: 433-443 (2002)), CT53518 (also known as MLN518) (Kelly, L. M., et. al., Cancer Cell 1: 421-432 (2002)), SU11248 (O'Farrell, A. M., et. al., Blood 101: 3597-3605 (2003)), SU5614 (Spiekermann, K., et. al., Blood 101: 1494-1504 (2003)), and SU5416 (Giles, F. J., et. al., Blood 102: 795-801 (2003)), have been shown to have antitumor activity. Collectively, these data suggest that FLT3 is an attractive therapeutic target for the development of kinase inhibitors for AML and other associated diseases.

Crystal structure of FMS-like tyrosine kinase


A camera includes a photo-taking lens, an automatic focus adjusting device for effecting the automatic focus adjustment of the photo-taking lens, an eye-gaze detecting device for detecting the photographer's eye-gaze position in a finder field corresponding to a photographing picture plane, and producing an eye-gaze detection signal corresponding to the eye-gaze position, a focus adjustment signal producing device for outputting a plurality of focus adjustment signals corresponding to a plurality of detection areas in the photographing picture plane, and a control signal producing device for producing a control signal for controlling the automatic focus adjusting means, on the basis of the eye-gaze detection signal and the focus adjustment signals. The control signal producing device produces the control signal on the basis of the plurality of focus adjustment signals corresponding to the plurality of detection areas when the eye-gaze position indicated by the eye-gaze detection signal is at a position between the plurality of detection areas.

1. Field of the Invention
This invention relates to a camera provided with eye-gaze detecting means suitable for use, for example, in a camera such as a still camera or a video movie camera endowed with the function of detecting an eye-gaze position in the photographing picture plane (of various positions in the photographing plane, the position of the portion the user is gazing at) and controlling the auto focusing operation of a photo-taking lens or controlling the exposure of film or an image pickup element.
2. Related Background Art
As cameras of this kind, there are known cameras in which what portion in the photographing picture plane the photographer should recognize as the main object is determined on the basis of the result of the eye-gaze detection and a photo-taking lens is driven by the use of an information value representative of the focus detection state corresponding to the object in the determined portion to thereby effect so-called auto focusing. There are also known cameras in which automatic exposure control is effected by the use of an information value representative of the luminance of an object in the portion recognized as the main object on the basis of the eye-gaze detection (such cameras are disclosed, for example, in Japanese Laid-Open Patent Application No. 63-94232, Japanese Laid-Open Patent Application No. 1-241511 and Japanese Laid-Open Patent Application No. 2-5).
However, in a camera wherein auto focusing is effected on the basis of the result of the eye-gaze detection, there may arise a problem as will be described below.
Suppose a case where, as shown in FIG. 7 of the accompanying drawings, a plurality of focus detection areas 1-3 are set in the photographing picture plane 10. Also assume that when the photographer gazes at between the focus detection area 1 and the focus detection area 2, the focus detection area nearer to the eye-gaze point is selected and a photo-taking lens is driven on the basis of an information value representative of the focus detection state in that area. Assuming that in the case of such a camera, the photographer's eye-gaze point is near the intermediate point a between the focus detection area 1 and the focus detection area 2 and, as shown in FIG. 8 of the accompanying drawings, the object distance D1 in the area 1 and the object distance D2 in the area 2 differ greatly from each other, the selected focus detection area will change over from the area 1 to the area 2 or from the area 2 to the area 1 simply if the eye-gaze point slightly moves unconsciously to right and left near the point a (the gaze of the human eye moves involuntarily even if one is gazing at one point). Each time the changeover takes place, the photo-taking lens is reciprocally driven between driven positions R1 and R2 as shown in FIG. 9 of the accompanying drawings, and this results in the waste of electric power. This is a problem which will likewise arise when the vicinity of the intermediate point b between the focus detection areas 2 and 3 is gazed at. Also, if the eye-gaze point is moved from the left end to the right end of the picture plane or conversely, the selected focus detection area will change over when the eye-gaze passes the point a and the point b and therefore, in conformity therewith, the driving of the photo-taking lens will take place suddenly. Thus, in the case of a camera for photographing moving images like a video movie camera, the object distance focused in a photographed moving image varies suddenly and therefore, that moving image becomes very unnatural one.
On the other hand, in a camera wherein automatic exposure is effected on the basis of the result of the eye-gaze detection, there may arise, for example, a problem as will be described below.
Assume that where as shown in FIG. 10 of the accompanying drawings, a plurality of photometry areas 11-13 are set in the photographing picture plane 10, a photometry area corresponding to the photographer's eye-gaze point is selected and exposure is determined on the basis of the luminance information in that area. In the case of such a camera, assuming that the photographer's eye-gaze point is near the intermediate point a between the photometry area 11 and the photometry area 12 and, as shown in FIG. 11 of the accompanying drawings, the object luminance B1 in the area 11 and the object luminance B2 in the area 12 differ greatly from each other, the selected photometry area will change over from the area 11 to the area 12 or from the area 12 to the area 11 simply if the eye-gaze point slightly moves unconsciously to right and left near the point a. Accordingly, simply if in spite of having gazed at a single object present near the eye-gaze point a, the photographer slightly moves the eye-gaze point, the exposure amount as the result of automatic exposure control may greatly vary to E1 and E2 as shown in FIG. 12 of the accompanying drawings. This is a problem which will likewise arise when the vicinity of the intermediate point b between the photometry areas 12 and 13 is gazed at. Also, if the eye-gaze point is moved from the left end to the right end of the picture plane or conversely, the selected photometry area will change over when the eye-gaze passes the point a and the point b and therefore, in conformity therewith, the exposure amount controlled will vary suddenly. Thus, in the case of a camera for photographing moving images like a video movie camera, the brightness of photographed moving images varies suddenly and unnaturally.


According to the present invention, a vehicular pop-up hood device includes a cylinder, a piston rod that can protrude from a front end of the cylinder, a gas generator to urge the piston rod, the gas generator provided at a side of a rear end of the cylinder, and a bracket to attach the cylinder to a vehicle body. The bracket includes a top portion engaged with the front end of the cylinder, and an overhanging portion for attachment to the vehicle body, the overhanging portion overhanging from the cylinder in a direction intersecting with an axial direction of the cylinder.

In recent years, there is being developed a vehicular pop-up hood device that pushes up a rear end portion of a hood when a vehicle collides with a collision body such as a pedestrian to receive the collision body with the hood and reduce an impact in a viewpoint of pedestrian protection etc.
In a vehicular pop-up hood device disclosed in patent document 1 (Japanese Patent Application Publication No. 2014-133535), actuators are arranged at both sides of a rear end portion of a hood. The actuators are activated at a collision or the like with a collision body, and push up a rear portion of the hood. The actuators each include a cylinder, a piston in the cylinder, a piston rod continuous to the piston, a gas generator, etc. When the gas generator is activated, the piston is pushed up, and the piston rod protrudes upward. The piston is pushed up until the piston comes into contact with a stopper portion (in patent document 1, referred to as front end wall portion) at an upper portion of the cylinder.
FIG. 3 and Paragraph [0023] in patent document 1 describe that the vehicular pop-up hood device (a hood panel flip-up device) is attached to a vehicle body member (a hood ridge reinforcement) through a bracket having a U-like cross-sectional shape. To be specific, the cylinder of the vehicular pop-up hood device is sandwiched between the bracket having the U-like cross-sectional shape and the hood ridge reinforcement of the vehicle body, and the bracket is fixed to the hood ridge reinforcement by bolts.
Patent document 2 (Japanese Patent Application Publication No. 2009-79761) describes that a vehicular pop-up hood device is entirely covered with a coating by fluorocarbon resin coating.
With the attachment structure like patent document 1, in which the vehicular pop-up hood device is attached by sandwiching the cylinder of the vehicular pop-up hood device between the bracket having the U-like cross-sectional shape and the hood ridge reinforcement of the vehicle body and by fixing the bracket to the hood ridge reinforcement by the bolts, it is required to firmly restrain a motion of the cylinder in the up-down direction when the vehicular pop-up hood device is activated. Hence, it is required to strongly sandwich and hold the cylinder between the bracket and the hood ridge reinforcement, to increase the strength and rigidity of the bracket, and to increase a cramping force of the bolts, resulting in an increase in cost.
Also, since the stopper portion (the front end wall portion) is required to strongly receive the piston when the piston comes into contact with the stopper portion, coupling between the stopper portion and the cylinder is required to be strong, resulting in an increase in cost.


A series of 5-(4-[2-substituted benzoxazolylmethoxy]benzyl)oxa- and thiazolidine-2,4-diones as antidiabetic and cholesterol lowering agents.

The present invention relates to certain compounds of formula (I), depicted below, having utility as hypoglycemic agents, methods for their use and pharmaceutical compositions containing them.
In spite of the early discovery of insulin and its subsequent wide-spread use in the treatment of diabetes, and the later discovery and use of sulfonylureas (e.g. chlorpropamide, tolbutamide, acetohexamide, tolazamide) and biguanides (e.g. phenformin) as oral hypoglycemic agents, the treatment of diabetes remains less than satisfactory. The use of insulin, necessary in about 10% of diabetic patients in which synthetic hypoglycemic agents are not effective (Type I diabetes, insulin dependent diabetes mellitus), requires multiple daily doses, usually by self injection. Determination of the proper dosage of insulin requires frequent estimations of the sugar in the urine or in the blood. The administration of an excess dose of insulin causes hypoglycemia, with effects ranging from mild abnormalities in blood glucose or coma, or even death. Treatment of non-insulin dependent diabetes mellitus (Type II diabetes) usually consists of a combination of diet, exercise, oral agents, e.g., sulfonylureas, and in more sever cases, insulin. However, the clinically available hypoglycemics are unfortunately fraught with other toxic manifestations which limit their use. In any event, where one of these agents may fail in an individual case, another may succeed. A continuing need for hypoglycemic agents, which may be less toxic or succeed where others fail, is clearly evident.
In addition to the hypoglycemic agents cited above, a variety of other compounds have been reported to possess this type of activity, as reviewed by Blank [Burger's Medicinal Chemistry, Fourth Edition, Part II, John Wiley and Sons, N.Y. (1979), pp. 1057-1080].
Schnur, U.S. Pat. No. 4,367,234 discloses hypoglycemic oxazolidinediones of the formula ##STR1## in which the phenyl ring is generally mono- or multisubstituted in the ortho/meta positions. Notably, with the exception of the 4-fluorophenyl analog, the parasubstituted derivatives are either inactive or possess a low level of hypoglycemic activity. Schnur, U.S. Pat. Nos. 4,332,952 and 4,342,771 further disclose a variety of similar oxazolidinedione hypoglycemic agents which are alternatively substituted at the 5-position with a heterocyclic group. These include certain furan, thiophene, pyrrole and pyridine derivatives.
Schnur, U.S. Pat. No. 4,617,312 discloses hypoglycemic thiazolidinediones of the formula ##STR2## where R.sup.c is lower alkyl, X.sup.a is F, Cl or Br, and Y.sup.a is hydrogen, chloro, lower alkyl or lower alkoxy. Notably, the compounds require ortho-substitution with an alkoxy group, and para-substitution is limited to hydrogen or halogen. Shoda et al. (Chem. Pharm. Bull., 30, 3563 (1982) describe the preparation of a series of 5-[4-(2-methyl-2-phenylpropoxy)benzyl]thiazolidine-2,4-diones as antidiabetic agents.
Kawamatsu et al., U.S. Pat. No. 4,340,605, disclose hypoglycemic compounds of the formula ##STR3## wherein R.sup.e is a bond or lower alkylene and when R.sup.d is an optionally substituted five- or six-membered heterocyclic group including one or two hetero-atoms selected from N, O and S, L.sup.1 and L.sup.2 may each be defined as hydrogen. Based on the lack of hypoglycemic and plasma triglyceride lowering activity of certain non-ether analogs, it has been suggested that the boxed portion of the structural formula, including the ether oxygen, represents an essential feature for useful activity in this series of compounds; Sohda et al., Chem. Pharm. Bull. Japan, Vol. 30, pp. 3580-3600 (1982).
Sohda et al. also describe the compound of the formula ##STR4## as having weak hypoglycemic and plasma triglyceride lowering activity.
Eggler et al., U.S. Pat. No. 4,703,052, discloses hypoglycemic thiazolidinediones of the formula ##STR5## where the dotted line represents an optional bond, R.sup.f is H, methyl or ethyl, X.sup.b is O, S, SO, SO.sub.2, CH.sub.2, CO, CHOH or NR.sup.k, R.sup.k is H or an acyl group and the numerous definitions of R.sup.g, R.sup.h, R.sup.i and R.sup.j include R.sup.g, R.sup.h and R.sup.i as hydrogen or methyl and R.sup.j as optionally substituted phenyl, benzyl, phenethyl or styryl.
Meguro et al., U.S. Pat. No. 4,725,610 disclose a series of hypoglycemic thiazolidinediones of the formula ##STR6##
EP 283,035A and EP 299,620A describe benzoxazole and benzofuran linked thiazolidinediones as antidiabetic agents.

Oxa- and thiazolidinedione hypoglycemic and hypocholesterolemic agents


One embodiment of the present invention is a composition for use in making edible biodegradable containers comprising water, pregelatinized and native starch, a first protein or natural polymeric compound, natural fibers, a wax emulsion, a mold release agent, a flavoring agent, and a coloring agent, wherein the composing consisting essentially of food grade materials.

1. Field of the Invention
The invention generally relates to a mix formulation for the production of edible, biodegradable, and compostable food packaging and service items and methods for use of said formulations.
2. Background
Conventional disposable food service items are commonly made from paper or paperboard (commonly coated or impregnated with a polymeric water-proofing material such as wax or polyethylene), or one of a variety of plastics (polystyrene is the most common). In addition, ovenable disposables are made from aluminum or CPET, commonly known as dual ovenable plastic.
During the introduction of Biosphere biodegradable compostable products, it was found that children often expressed a desire to eat the articles presented. When asked, adults also expressed an interest in edible packaging or food-service items. Edible, starch-based food service items which were greeted with considerable public enthusiasm at the 1994 Winter Olympic Games in Lillehammer, Norway; after use, those items were fed to livestock, eliminating a large source of waste. Home and industrial bakers have expressed a desire for edible molding devices for cakes, cupcakes, muffins, tarts, pies, and the like, to replace the metal and paper items currently in use.
In addition to the intrinsic appeal of edible packaging materials to children and other consumers, there is a growing recognition that the environmental costs of using "cheap" plastic materials for packaging may be quite high. The expected lifetime of a polystyrene cup, for example, is about 500 years, and each American disposes an average of about 100 cups per year. Polystyrene is made by chemical processing of benzene and ethylene, both byproducts of the petroleum industry, and thus both nonrenewable resources. Although the environmental record of the petroleum industry has improved greatly since the mid-twentieth century, extraction and processing of petroleum for fuel and chemical production remain recognized environmental problems. Questions have also been raised about the wisdom of using a limited natural resource (fossil hydrocarbon stocks) to produce disposable items (which exacerbate waste handling problems) rather than reserving the resource for production of durable goods.
United States Government sources indicate that packaging (of all types) makes up 32 percent of the municipal solid waste stream by weight. Food packaging makes up about 9 percent of the waste stream. Costs of disposal of municipal wastes are likely to increase as landfill regulations become more stringent, current sites are filled and replaced by (usually) more distant sites, and waste transportation costs increase (along with fuel costs).
Pet food packaging also contributes appreciably to the waste stream. The total annual worldwide market for pet food packaging has been estimated to exceed $500 million, with increasing emphasis on smaller packaging, including portion-sized packages. As in all industries, the smaller the quantity of product per unit sold, the greater the ratio of packaging volume to product volume; the quantity of pet food packaging being used is thus growing at a higher rate than the quantity of pet food itself.
Materials that are impervious to moisture and impermeable to oxygen and other gases include conventional plastics, metals, glass, and plastic-coated paper or paperboard. Of these, metal, glass, paperboard, and molded plastics typically provide structural protection of the packaged items as well as barrier properties, whereas plastic films and plastic-coated papers mainly provide barrier protection rather than structural protection. Typically much more mass is required to obtain the structural rigidity required of packaging than is required to obtain suitable barrier properties alone. None of these materials are biodegradable or compostable. To the extent that they enter the disposal waste stream (i.e., that they are not recycled), these materials are persistent; they will remain in landfills even where oxygen and moisture are provided to encourage biodegradation.
In addition to waste disposal concerns, some current research suggests that certain chemicals (phthalates and other plasticizers) used in the manufacture of plastics may have detrimental effects on the environment and on human reproductive systems, even at extremely low concentrations, by affecting the endocrine (hormone) system in humans and many other animal species. The observations suggest that, in both wildlife and humans, very low concentrations of these compounds can mimic or interfere with hormones that play important roles in embryonic development, resulting in effects such as hermaphroditism in gastropods; feminization of fish, alligators, and some mammals; malformations or morbidity in amphibians, fish, and birds; and various effects in human developmental and reproductive biology. Although the research and many of the conclusions that have been drawn from it are controversial, the FDA and some Japanese and European regulatory agencies are considering bans or additional regulations on certain phthalates. Regardless of how this debate is resolved in the future, there is currently increasing public concern about the safety of plastics and the plasticizers that are used to improve their physical properties.
The desire to use disposable packaging materials that are biodegradable and compostable has been steadily increasing in the last decade. As recently as March, 2003, Taiwan outlawed the use of polystyrene foam in disposable packaging. China's major cities (e.g., Beijing and Shanghai) have also outlawed the use of polystyrene foam in disposable packaging. Commenting on solid waste policy in the United States, the web site of American Society of Civil Engineers says that "the problem of over consumption should be addressed, with the goal of reducing the production and consumption of unnecessary goods, packaging and throwaways. Toxic materials used in products and packaging and produced as byproducts in production processes should be minimized."
Unlike plastics, paper and paperboard are made from wood pulp, which is a renewable material. The regeneration time, however, for wood fiber—the time required to grow a tree—is substantial, and the chemical processing needed to produce white ("bleached") fibers has been recognized to be detrimental to the environment. The use of unbleached and recycled fibers helps alleviate these environmentally detrimental activities, but the use of slow-growing trees as a fiber source when many agricultural byproduct sources are available is in itself questionable.
Further, in the current art, starch-based food service articles typically contain two or three major phases: a matrix material (mainly starch) that contains inorganic filler materials and/or fibrous materials. The mechanical properties of the starch matrix material are critical to the performance of these articles. Baked unmodified starch is typically quite fragile and brittle when dry, but relatively soft and pliable when the starch contains 5% to 10% moisture. In current practice, fiber is often added to the formulation to increase the flexural strength and fracture energy of starch-based items, especially during the period immediately after demolding, when the moisture content of the starch is very low. Even with the addition of significant amounts (10% or more) of fiber, however, starch-based articles are commonly very brittle immediately after demolding or when stored for extended periods in dry environments (heated buildings in winter, air conditioned buildings in summer, desert environments any time of year). Brittle failure of starch-based articles thus continues to present problems during the manufacturing process (especially before coatings or laminated films are applied) and when the articles are used in dry environments.
Moreover, in the current art, inorganic mineral fillers (e.g., calcium carbonate, silica, calcium sulfate, calcium sulfate hydrate, magnesium silicate, micaceous minerals, clay minerals, titanium dioxide) are often included in formulations used to produce starch-based biodegradable food service articles. These fillers are not, however, biodegradable. Marketing claims made for products using these materials as fillers point out that the materials are natural, renewable, and environmentally benign. However, there are inherent environmental costs associated with the mining (or synthesis) and processing of all inorganic filler materials.
Finally, in the current art, the most commonly used fiber in starch-based food service articles is wood-pulp fiber (similar to the paper based articles). As the main source material for the paper industry, it is readily available, is consistent in quality and material properties, and has the main properties needed to serve as structural elements in the finished food service articles. The use, however, of slow-growing trees as a fiber source when many agricultural byproduct sources are available is, as set forth above, in itself questionable.
Accordingly, there is a need for an improved system for producing edible, biodegradable, and compostable disposable items that can serve the full range of uses to which containers, plates, trays, and bowls are usually put. Consumers clearly would benefit from the introduction of a new edible food service and packaging material. Society at large would clearly benefit from an overall reduction in the amount of food packaging materials in the municipal solid waste stream.
Further, there is a need to reduce the proportion of persistent, non-biodegradable food packaging in the municipal waste stream. Development of packaging systems that combine edible, compostable, and biodegradable materials for structural rigidity with minimal amounts of plastic film or plastic-coated paper for protection from water, water vapor, oxygen, and contaminants would be beneficial.
Further, development of packaging materials made entirely from natural, edible ingredients would reduce both environmental and human health effects of plasticizers, to whatever extent they are eventually shown to occur. Until the debate over the issue is resolved, edible packaging materials may serve as an alternative to plastics for concerned consumers.
There is also a need for an improvement in the current art that will replace mineral fillers with fully biodegradable and renewable plant-based organic materials that serve the same role as traditional mineral fillers. Even greater benefit is available if the filler material is currently produced as a byproduct of the production of another agricultural material.
Finally, there is also a need for methods and formulations that incorporate fibrous materials from annually grown non-wood plants, and particularly from materials that are byproducts of commodities already in production.

Composition for use in edible biodegradable articles and method of use


The present disclosure provides a method of manufacturing a semiconductor device. The method includes forming a fin structure in which first semiconductor layers and second semiconductor layers are alternately stacked; forming a sacrificial gate structure over the fin structure; etching a source/drain region of the fin structure, which is not covered by the sacrificial gate structure, thereby forming a source/drain trench; laterally etching the first semiconductor layers through the source/drain trench; forming an inner spacer layer, in the source/drain trench, at least on lateral ends of the etched first semiconductor layers; forming a seeding layer on the inner spacer layer; and growing a source/drain epitaxial layer in the source/drain trench, wherein the growing of the source/drain epitaxial layer includes growing the source/drain epitaxial layer from the seeding layer.

The semiconductor integrated circuit (IC) industry has experienced exponential growth. Technological advances in IC materials and design have produced generations of ICs where each generation has smaller and more complex circuits than the previous generation. In the course of IC evolution, functional density (i.e., the number of interconnected devices per chip area) has generally increased while geometry size (i.e., the smallest component (or line) that can be created using a fabrication process) has decreased. This scaling down process generally provides benefits by increasing production efficiency and lowering associated costs. Such scaling down has also increased the complexity of processing and manufacturing ICs.
Recently, multi-gate devices have been introduced in an effort to improve gate control by increasing gate-channel coupling, reduce OFF-state current, and reduce short-channel effects (SCEs). One such multi-gate device that has been introduced is the gate-all-around field effect transistor (GAA FET). The GAA FET device gets its name from the gate structure which can extend around the channel region providing access to the channel on two or four sides. GAA FET devices are compatible with conventional complementary metal-oxide-semiconductor (CMOS) processes and their structure allows them to be aggressively scaled while maintaining gate control and mitigating SCEs. GAA FET devices provide a channel in a stacked nanosheet configuration. Integration of GAA features around stacked nanosheets can be challenging. For example, in a stacked nanosheet GAA process flow, inner spacer layer formation can be an important process to reduce capacitance and prevent leakage between gate stacks and source/drain (S/D) regions. However, the inner spacer layer may cause difficulties in subsequent S/D epitaxial feature formation, such as voids or other interior defects during epitaxial growth, because of limited available semiconductor seed area. Therefore, while the current methods have been satisfactory in many respects, challenges with respect to performance of the resulting device may not be satisfactory in all respects.

Method of manufacturing a source/drain feature in a multi-gate semiconductor structure

TAIWAN SEMICONDUCTOR MANUFACTURING CO., LTD


Portable workstation or desk apparatus and methods. In one embodiment, a portable workstation is comprised of a plurality of components including a work surface or upper element, a stem or support element, and an anchor or base element. In one variant, the work surface element (and/or the base element) can be mounted to the stem element in first and second configurations. The various configurations provides a substantially level work surface (relative to the base) or a substantially inclined work surface, and/or varying degrees of offset relative to the base.

1. Field of Invention
The present invention relates generally to portable workstations or surfaces, and more particularly in one exemplary aspect to a collapsible portable desk for various uses such as reading or supporting a computerized device.
2. Description of Related Technology
Flexibility in modern day travel enables those who desire to travel vast distances in a short amount of time. For example, it is not unusual for a business person to travel from one continent to another in a matter of one or two days solely to effectuate a business transaction with a manufacturer or distributor. Advances in the portability of electronic devices allows travelers to bring a wide array of such devices (e.g., laptop computers, portable DVD players, cellular phones, tablet readers, etc.) when traveling. Even those traveling short distances may have a need to bring a particular portable electronic device for business purposes or for pleasure. A traveler may choose to use a particular portable device in a variety of different venues, e.g., in a car, train, airplane, airport, etc.
One challenge in using portable electronic devices while in transit can be situating it in a feasible and/or comfortable position for use by the traveler. With respect to at least a laptop computer, other challenges can relate to dissipation of the heat generated by the computer (which can be appreciable due to, e.g., the large batteries carried in many laptops and the computer's comparatively small dimensions and lack of airflow), weight of the computer, and balancing the computer on the user's legs or other body parts.
Moreover, indigenous mechanisms for supporting a user's computer, papers, etc. are often cramped and not optimized. For instance, the well known fold-down seatback trays used commonly in commercial aircraft are often limited to a flat (horizontal) position, and typically are not ergonomically positioned so that extended use is uncomfortable for the passenger.
Another need is to have a stable, comfortable, and portable work surface while waiting for extended periods during travel (e.g., for boarding of a plane or train, etc.). Most airports and train terminals have limited workspace, especially for example at airline gates. This causes users wishing to access their electronic device to dispose it on their lap or hold it in their hands, which is not conducive to productive or extended use.


In some embodiments, a mobile media device enclosure can include: (a) an enclosure having an interior, an exterior, a top side, a bottom side, a right side, and a left side, the interior configured to form a cavity, the cavity is sized to retain a mobile media device therein; (b) a vertical boundary, the vertical boundary having a substantially vertical orientation and configured to substantially bisect the mobile media device enclosure from the top side to the bottom side; and (c) a horizontal boundary, the horizontal boundary having a substantially horizontal orientation and configured to substantially bisect the mobile media device enclosure from the left side to the right side. The vertical boundary and the horizontal boundary are further configured to substantially divide the mobile media device enclosure into four sections. Each of the four sections is elastically coupled to two other sections of the four sections. Other embodiments and related methods are also disclosed herein.

Advancing technology has made portable electrical devices (i.e., mobile media devices) increasingly popular and has given such electrical devices an ever-increasing array of capabilities. Some electrical devices, such as digital music and video players, cellular phones, personal digital assistants, handheld digital computers, and the like, include the capability to display images or videos. It is possible to view the images or videos while holding such video-capable devices in one's hand, but it would often be more convenient and more comfortable to set down such electrical devices and have them maintain a position in which the images and videos can be viewed easily. Examples of video-capable devices are the iPod® or iPhone® or iTouch® product by Apple Inc. of Cupertino, Calif. Another example of a video-capable device is the Blackberry® product by Research In Motion (RIM) of Waterloo, Ontario, Canada.
Furthermore, most portable electrical devices include display or touch screens and/or control mechanisms. It would be convenient for the user of such electrical devices if a protective case allowed easy viewing of the display screen from a distance and operation of the electrical device, without requiring the user to hold the electrical device or remove it from the case.
Accordingly, a need exists for a case for an electrical device that both protects the electrical device and allows it to maintain a hands-free operating and viewing position.
For simplicity and clarity of illustration, the drawing figures illustrate the general manner of construction, and descriptions and details of well-known features and techniques may be omitted to avoid unnecessarily obscuring the invention. Additionally, elements in the drawing figures are not necessarily drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of embodiments of the present invention. The same reference numerals in different figures denote the same elements.
The terms "first," "second," "third," "fourth," and the like in the description and in the claims, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments described herein are, for example, capable of operation in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "include," and "have," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, device, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, system, article, device, or apparatus.
The terms "left," "right," "front," "back," "top," "bottom," "over," "under," and the like in the description and in the claims, if any, are used for descriptive purposes and not necessarily for describing permanent relative positions. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the invention described herein are, for example, capable of operation in other orientations than those illustrated or otherwise described herein.
The terms "couple," "coupled," "couples," "coupling," and the like should be broadly understood and refer to connecting two or more elements or signals, electrically, mechanically or otherwise. Two or more electrical elements may be electrically coupled, but not mechanically or otherwise coupled; two or more mechanical elements may be mechanically coupled, but not electrically or otherwise coupled; two or more electrical elements may be mechanically coupled, but not electrically or otherwise coupled. Coupling (whether mechanical, electrical, or otherwise) may be for any length of time, e.g., permanent or semi-permanent or only for an instant.
"Electrical coupling" and the like should be broadly understood and include coupling involving any electrical signal, whether a power signal, a data signal, and/or other types or combinations of electrical signals. "Mechanical coupling" and the like should be broadly understood and include mechanical coupling of all types. The absence of the word "removably," "removable," and the like near the word "coupled," and the like does not mean that the coupling, etc. in question is or is not removable.

Mobile media device enclosure, method of use of mobile media device enclosure, and method of providing mobile media device enclosure


A protective material for a molten carbonate fuel cell, which comprises a ceramic comprising an oxide material capable of chemically reacting with an electrolyte used in the molten carbonate fuel cell for generating electric energy by consuming hydrogen formed from a raw fuel such as hydrocarbons, or with a substance formed from the electrolyte. The protective material protects a reforming catalyst or component materials of the fuel cell power generation system from the electrolyte or the substance formed from the electrolyte.

1. Field of the Invention
The present invention relates to a protective material capable of protecting a reforming catalyst and component materials from an electrolyte, in a molten carbonate fuel cell for generating electric energy by consuming hydrogen, which is formed from a raw fuel such as hydrocarbons.
2. Description of the Prior Art
FIG. 1 shows a perspective view of a major part of a conventional internal reforming type molten carbonate fuel cell disclosed in, for instance, Japanese Patent Application Laid-Open (KOKAI) No. 60-32255 (1985). In the figure, 1 denotes an electrolyte matrix composed of a porous ceramic with spaces therein filled with a carbonate used as an electrolyte, 2 denotes a fuel electrode (anode) composed of porous nickel or the like, and 3 denotes an oxidizing agent electrode (cathode) composed of a porous material such as nickel oxide. The fuel electrode 2 and the oxidizing agent electrode 3 are disposed opposite to each other, with the electrolyte matrix 1 therebetween, and these constitute a single unit of a cell. In the figure, 4 denotes an oxidizing agent passage provided for the oxidizing agent electrode 3, 5 denotes a perforated fuel-side spacer disposed in contact with the fuel electrode 2, and 6 denotes a rib provided perpendicularly to the fuel-side spacer 5, with the spacer 5 and the ribs 6 defining fuel gas passages 7. By 8 is denoted a fuel reforming catalyst packed in the fuel gas passages 7.
FIG. 2 shows a system diagram illustrating the construction of a fuel cell power generation system employing an external reforming type molten carbonate fuel cell body disclosed in Japanese Patent Application Laid-Open (KOKAI) No. 60-230365. In the diagram, a fuel treating device 9 and an air supply device 10 are connected to a molten carbonate fuel cell body 11. A combustor 12 is provided for oxidizing a fuel gas not reacted in the fuel cell body 11, a heat exchanger 13 is provided for removing surplus heat generated in the fuel cell body 11 to the exterior of the system, and a circulating blower 14 is provided for circulating an oxidized gas, which serves as a coolant.
Operations of the fuel cells will now be explained. In the internal reforming type fuel cell, the fuel reforming catalyst 8 provided in the fuel gas passages 7 adjacent to the fuel electrode 2 is used to induce a reforming reaction of a hydrocarbon or alcohol contained in the fuel gas, thereby forming hydrogen. Hydrogen thus formed through the reforming reaction in the fuel gas passages 7 is oxidized to water by an electrochemical reaction at the fuel electrode 2 adjacent to the passages 7. Part of the energy generated on the oxidation is converted to electric energy. For a long, stable operation of the internal reforming type fuel cell, therefore, it is essential to maintain a stable activity of the reforming catalyst 8 for a long time. However, in the conventional internal reforming type fuel cell, the reforming catalyst 8 is held adjacent to the fuel electrode 2 and, therefore, adhesion of the electrolyte to the reforming catalyst 8 is inevitable. On the other hand, the external reforming type fuel cell power generation system operates as follows. In a conventional fuel cell power generation system as shown in FIG. 2, the electrolyte or a substance formed therefrom which is contained in the fuel gas or oxidized gas discharged from the molten carbonate fuel cell body 11 is fed, as it is, downstream through the power generation system. This causes corrosion of component members of piping or apparatus, or lowering in the activity of the reforming catalyst. At a low-temperature part, in particular, problems such as solidification of the electrolyte and clogging of passages are generated. Thus, the conventional fuel cell power generation system has generally had the problem of reduction of the characteristics of the component apparatuses and the problem of a short service life.
Namely, in the conventional molten carbonate fuel cell power generation system as mentioned above, whether the molten carbonate fuel cell body is of the internal reforming type or of the external reforming type, the electrolyte evaporated or spattered into the reaction gas in the fuel cell body or the substance formed from the electrolyte will adhere to the materials constituting the fuel cell power generation system inclusive of the fuel cell body itself, to impair the characteristics of the constituent materials, thereby making it difficult to operate the system for a long time.
More particularly, for instance, the internal reforming type fuel cell body has the following problem. The reforming catalyst 8 is reduced in performance when contacted by the electrolyte held in the electrolyte matrix 1 or by decomposition products of the electrolyte. This arises from the migration of the electrolyte, through evaporation or the like, from the matrix 1 to the place where the reforming catalyst 8 is disposed. The degradation of the performance of the reforming catalyst 8, for instance, a nickel catalyst takes place as follows. When nickel particles (about 200 .ANG. in diameter) makes contact with the electrolyte, nickel dissolves in the electrolyte as NiO, and growth of particles occurs. The particles grow to a particle size of about 500 to 3000 .ANG., with a reduction in surface area. Alternatively, the adhered electrolyte lowers the catalytic activity of the catalytically active substance (nickel particles). Thus, the performance of the catalyst is degraded. The dissolution of NiO in the electrolyte is discussed in literature [C. E. Baumgartner, "Solubility and Transport of NiO Cathodes in Molten Carbonate Fuel Cells", J. of American Ceramic Society, Vol. 69 (1986), pp. 162-168].
On the other hand, the use of the external reforming type fuel cell body has the following problems. First, the vapor of the electrolyte reacts with a main constituent material of piping or apparatus, for example, stainless steel parts at high-temperature, to form a corroded layer, thereby enbrittling or weakening the constituent material. In addition, adhesion or solidification of the electrolyte occurs at low-temperature parts to cause clogging, especially at narrow parts. Besides, as a total effect of the above, the electrolyte causes reduction in the characteristics and service life of the circulating blower 14, the heat exchanger 13, etc. For example, in a single-cell test on molten carbonate fuel cells, adhesion or solidification of the electrolyte was observed at narrow parts, particularly at an outlet pipe on the fuel gas side. For a steady operation, it was necessary to clean the piping, for instance, at a time interval of 1000 to 3000 hours.

Protective material for molten carbonate fuel cell


A memory device such as a 6F2 memory device includes isolation trenches that are formed generally parallel to and along associated strips of active area. A conductive bit line is recessed within each isolation trench such that the uppermost surface of the bit line is recessed below the uppermost surface of the base substrate. A bit line contact strap electrically couples the bit line to the active area both along a vertical dimension of the bit line strap and along a horizontal dimension across the uppermost surface of the base substrate.

The present invention relates in general to memory devices and in particular to memory devices having conductive lines buried in isolation regions.
Dynamic random access memory (DRAM) memory has enjoyed popular success over other types of memory technology because of its low cost and simple memory cell layout, which promotes scalability. A DRAM memory cell is capable of storing one bit of information and is constructed using only one memory cell transistor and one memory cell capacitor. As such, this memory cell is often referred to as a one-transistor one-capacitor (1T1C) cell. In a typical memory device, collections of 1T1C memory cells are grouped together by bit lines and word lines forming a memory array.
The industry is continually striving to produce DRAM memory devices that provide increased storage capacity, yet provide comparable to improved operational performance. Increase in circuit density is often the result of an ability to manufacture a given device in a smaller physical space than previously possible, allowing an increase in packing density. However, device density in DRAM memory is limited by both the resolution capability of available photolithographic equipment (feature size) and the area consumed by each memory cell in a given memory array.
One known DRAM memory device stacks storage capacitors above memory cells. For example, memory cells are fabricated by forming word line gate stacks over a semiconductor substrate. Bit lines are subsequently fabricated by forming a metal line in a passivating insulating layer over the semiconductor substrate. A bit line is electrically coupled to an associated memory cell by forming a via that passes through one or more layers of the memory device to a bit line contact on the semiconductor substrate. Capacitor structures are also formed over the semiconductor substrate and are electrically coupled an associated memory cell by forming a via through one or more semiconductor layers. As such, for each memory cell, one via is required to connect the bit line to the memory cell and a second via is required to connect the capacitor structure to the memory cell. Under such an arrangement, the capacitor is typically stacked over the bit line. However, this requires a relatively deep via having contact openings that are difficult to form and hard to fill. For example, poor step coverage and adhesion may occur resulting in poor electrical performance and increased contact resistance. Accordingly, there is a continuing need for improved memory.
The amount of charge that a storage capacitor can store is generally related to the amount of storage node surface area. As DRAM dimensions grow smaller, there is an ever-increasing need to maintain storage capacitance values despite more tightly packed circuits. However, the minimum realizable area of the vias required to connect the bit line and capacitor to the memory cell is limited by the minimum realizable feature size. Accordingly, for a given area, space that would otherwise be available for capacitor structures is required to provide the bit line and bit line contacts. As packing density in DRAM structures increases, the via size thus serves to limit the area available for capacitor structures. Accordingly, there is a continuing need for improved or alternative memory device structures.
The present invention overcomes the disadvantages of previously known semiconductor devices by providing a memory device with a trench buried bit line.
According to one embodiment of the present invention, a memory device such as a 6F2 memory device includes isolation trenches that are formed generally parallel to and along associated strips of active area. A conductive bit line is recessed within each isolation trench such that the uppermost surface of the bit line is recessed below the uppermost surface of the base substrate. A bit line contact strap electrically couples the bit line to the active area both along a vertical dimension of the bit line strap and along a horizontal dimension across the uppermost surface of the base substrate.


The present invention is the invention for providing a guidance service by using a robot. For example, the robot may provide the guidance service in an airport. The robot may receive a destination, acquire a movement path from a current position to the destination, and transmit the movement path to the mobile terminal. The mobile terminal may receive the movement path from the robot and display a guidance path representing a movement path and a user path representing a position movement of the mobile terminal and overlapping the guidance path.

Recently, as deep learning technology, self-driving technology, automatic control technology, and Internet of things (IoT) advance, it is possible to implement intelligent robots. Intelligent robots are disposed at public places such as airport, and thus, it is possible to provide users with various information and services.
Each technology will be described below in detail. Deep learning corresponds to the field of machine learning. The deep learning is technology which allows a program to perform similar determination on various situations, instead of a method where a condition and a command are previously set in a program. Therefore, according to the deep learning, computers may think similar to brains of humans and may analyze massive data.
Self-driving is technology where a machine determines and moves autonomously to avoid an obstacle. According to the self-driving technology, a robot autonomously recognizes and moves a position through a sensor to avoid an obstacle.
The automatic control technology denotes technology where a machine feeds back a measurement value, obtained by inspecting a machine state, to a control device to automatically control an operation of the machine. Therefore, control may be performed without manipulation by a user, and control may be automatically performed so that a desired control target reaches a desired range.
IoT denotes intelligent technology and service where all things are connected to one another over Internet and information exchanges between a user and a thing and between a thing and a thing. Devices connected to Internet through IoT transmit or receive information to perform autonomous communication, without the help of a user.
There is a global positioning system (GPS) for calculating a current position of a user. The GPS performs an arithmetic operation on a distance between a GPS satellite and a GPS receiver to calculate coordinates. In order to determine a current position, three or more GPS satellites are needed. Also, when radio waves are received from three or more GPS satellites, a relatively accurate position may be checked.