A coated film and a coated glass improved in the resistance to fouling derived from water and oil repellency, and in the durability, the abrasion resistance, and the exfoliation of stacked outer layer, are provided by a specific coating composition having at least one component (a) selected from organosilanes, hydrolyzates of the organosilanes, and condensates of the organosilanes, and component (b) containing a silyl group wherein one of silicon atoms bonded with a hydrolytic group and/or a hydroxy group.

The present invention relates to a coating composition improved in the resistance to fouling derived from water and oil repellency, the durability and the abrasion resistance, and in the release and exfoliation of stacked outer layer, and to a coated film and glass each having a coating layer comprised thereof.
Organosilane coating materials have technically been developed for use as maintenance-free coating materials which are advantageous for the resistance to weather (and sunlight), fouling, and so forth. The demand for improving the performance of organosilane coating materials is overwhelmingly increased. Therefore, it is now desired to provide coating materials which are improved in the coating appearance, the adhesiveness, the resistance to weather, heat, alkalis, organic chemicals, moisture, and (hot) water, the insulating property, the abrasion resistance, the resistance to fouling, and so forth.
Particularly for improving the resistance to fouling, it is known to make the surface of a coating hydrophilic. However, hydrophilization is a treatment to enhance the effect of washing and removing out of contaminants. Therefore, only in the case that the effect of washing overcomes the contamination, the hydrophilized coating shows the resistance to fouling. On the contrary, by the method of imparting the water and oil repellency to the coating layer, it is able to prevent the adhesiveness of both of hydrophilic and lipophilic contaminants. In prior art, addition of oils or surfactants to the coating composition is made in order to impart the water and oil repellency to the coating layer. By the addition of those, it is not able to maintain the abrasion resistance for a long period of time.
Further disclosed are a composition adapted for use as a composition which satisfies the requirements for performance of an organosilane coating material and composed mainly of a partial condensate of organosilane, a dispersion of colloidal silica, and an acrylic resin denatured by a silicone (See Japanese Patent Laid-open Publication (Sho) 60-135465), a composition composed mainly of a condensate of organosilane, a chelate compound of zirconium alkoxide, and a hydrolytic silyl-based vinyl resin (Japanese Patent Laid-open Publication (Sho) 64-1769), and a compound composed mainly of a condensate of organosilane, a colloidal alumina, and a hydrolytic silyl-based vinyl resin (See U.S. Pat. No. 4,904,721).
However, coatings made of the compositions disclosed in (Japanese Patent Laid-open Publication (Sho) 60-135465) and U.S. Pat. No. 4,904,721 have the disadvantage that their glittering property may be declined when they are exposed to ultraviolet light for a considerable length of time. Also, the composition disclosed in (Japanese Patent Laid-open Publication (Sho) 64-1769) is low in the storage stability; it may easily be turned to gel within a short period of time when its solid density is increased.
We, the inventors, have invented a composition for coating which includes a hydrolyzate and/or a partial condensate of organosilane, a vinyl resin having a silyl group wherein silicon atoms are bonded with a hydroxy group and/or a hydrolyzate, a metallic chelate compound, xcex2-diketone and/or xcex2-ketoester (See Japanese Patent Laid-open Publication (Hei) 5-345877). Since this composition has a favorable balance over the coating characteristics required for any organosilane coating material, new coating materials having more improvement in the coating characteristics such as the water and oil repellency and the smoothness of the surface of the coating layer shall be required.
Moreover, a coated film having photocatalytic function is proposed, formed by coating a film substrate. For example, in Japanese Patent Laid-open Publication (Hei) 9-227161, a self-cleaning film having a surface layer containing substantially transparent particles of a photocatalytic metal oxide on a film substrate surface, is disclosed. Also, a photocatalytic sheet having a photocatalytic coating formed on its upper surface and provided at its lower surface with an adhesive coating for attaching to another device or material to offer a photocatalytic function is disclosed in Japanese Patent Laid-open Publication (Hei) 9-313887. However, these coated films or sheets show the resistance to fouling by the highly hydrophilicity derived from photocatalyzation. Therefore, those show the effect only by irradiation and effect of removing out of contaminants only by washing or raining.
Moreover, an anti-fogging window glass having a surface layer provided on a window glass substrate and containing substantially transparent particles of a photocatalytic oxide is disclosed in Japanese Patent Laid-open Publication (Hei) 9-227161. The above glass may however show the effect only by irradiation and watering (raining), and easily fouled by oils because of its lipophilicity.
Also, a coated glass having a surface layer (10 to 200 nm thickness) composed of a photocatalytic metal oxide such as titanium dioxide provided on a glass substrate is disclosed in Japanese Patent Laid-open Publication (Hei) 9-235140. The coated glass is however regarded as inferior to the durability because it is provided without binder. Further, in Japanese Patent Laid-open Publication (Hei) 9-227159, an automobile window glass having a surface layer containing substantially transparent materials of a photocatalytic semiconductor on a glass substrate surface, is disclosed. The window glass is however regarded as inferior to the durability because of containing no binder.
The present invention has been invented in view of overcoming the foregoing technical drawbacks of the prior arts and its object is to provide a coating composition improved in the resistance to fouling derived from water and oil repellency, the durability and the abrasion resistance, and to a coated film and glass each having a coating layer comprised thereof.
1. A coating composition containing at least one component (a) selected from organosilanes, hydrolyzates of the organosilanes, and condensates of the organosilanes represented by Formula 1
(R1)nSi(OR2)4- nxe2x80x83xe2x80x83(1)
(wherein, R1 is a monovalent organic group having 1 to 8 carbon atoms: when two exist, they are either identical to or different from each other; R2 is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms: when two exist, they are either identical to or different from each other; and n is an integer ranging from 0 to 2);
and a polymer component (b) having a silyl group wherein silicon atoms are bonded with a hydrolytic group and/or a hydroxy group (referred to as a fluoropolymer having a silyl group hereinafter);
wherein the component (b) comprises a substance selected from polymers having a structural unit (b-1) expressed by Formula 2 (referred to as structural unit (b-1) hereinafter)
xe2x80x83(wherein, R3 to R5 are CmY2m+1, m is an integer ranging from 0 to 5, and Y is selected from F, H, and Cl separately) and/or a structural unit (b-2) expressed by Formula 3 (referred to as structural unit (b-2) hereinafter)
xe2x80x83(wherein, Rf is an alkyl group or an alkoxyalkyl group having fluorine atoms and R3 to R5 are analogous to those in Formula 2 or may be modified without departing from the term of analogy).
2. A coated film having a coating layer comprised of a coating composition according to item 1.
3. A coated film having a coating layer comprised of the composition (i) or (ii), wherein,
the composition (i) is a coating composition containing at least one component (a) selected from organosilanes, hydrolyzates of the organosilanes, and condensates of the organosilanes represented by Formula 1
(R1)nSi(OR2)4- nxe2x80x83xe2x80x83(1)
(wherein, R1 is a monovalent organic group having 1 to 8 carbon atoms: when two exist, they are either identical to or different from each other; R2 is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms: when two exist, they are either identical to or different from each other; and n is an integer ranging from 0 to 2), and
the composition (ii) is a coating composition containing the component (a) and a polymer component (bxe2x80x2) having a silyl group wherein silicon atoms are bonded with a hydrolytic group and/or a hydroxy group; and a coating layer comprised of a coating composition according to item 1 formed thereon.
4. A coated glass having a coating layer comprised of a coating composition according to item 1.
5. A coated glass having a coating layer comprised of the composition (i) or (ii), wherein,
the composition (i) is a coating composition containing at least one component (a) selected from organosilanes, hydrolyzates of the organosilanes, and condensates of the organosilanes represented by Formula 1
(R1)nSi(OR2)4- nxe2x80x83xe2x80x83(1)
(wherein, R1 is a monovalent organic group having 1 to 8 carbon atoms: when two exist, they are either identical to or different from each other; R2 is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms: when two exist, they are either identical to or different from each other; and n is an integer ranging from 0 to 2), and
the composition (ii) is a coating composition containing the component (a) and a polymer component (bxe2x80x2) having a silyl group wherein silicon atoms are bonded with a hydrolytic group and/or a hydroxy group; and a coating layer comprised of a coating composition according to item 1 formed thereon.
The present invention will now be described in a sequence.
The composition (I) is a coating composition containing the following components (a).
Component (a)
The component (a) is at least a substance selected from organosilanes denoted by Formula 1 (referred to as organosilanes (1) hereinafter), hydrolyzates of the organosilanes (1), and condensates of the organosilanes (1) More specifically, the component (a) may be of one of the three groups or a mixture of any two groups or a mixture of all the three groups.
It should be noted that the hydrolyzate of an organosilane (1) is not limited to a particular one where all the OR2 groups, generally two to four, in the organosilane (1) have been hydrolyzated but may be prepared where one or two or more of the groups have been hydrolyzated or may be a mixture of those groups.
The condensate of an organosilane (1) has a Sixe2x80x94Oxe2x80x94Si bond where the silanol group in a hydrolyzate of the organosilane (1) has been condensed. It is not mandatory to condense all the silanol groups. The concept of a condensate of the organosilane (1) according to the present invention includes one where only a few of the silanol groups have been condensed and a mixture of condensates whose levels of condensation are different.
In Formula 1, characteristic examples of the monovalent organic group of R1 containing 1 to 8 carbon atoms are, for example, an alkyl group such as methyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-hexyl, n-heptyl, n-octyl, or 2-ethylhexyl; an acyl group such as acetyl, propionyl, butyryl, valeryl, benzoyl, trioyl, or caproyl; a vinyl group; an aryl group; a cyclohexyl group; a phenyl group; an epoxy group; a glycidyl group; a (meth)acryloxy group; an ureide group; an amide group; a fluoroacetoamide group; an isocyanate group and a fluoroalkyl group as well as their substituent derivatives.
The substituent group in the substituent derivative of R1 maybe selected of a set of halogen atoms, a substituted or not-substituted amino group, a hydroxy group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth)acryloxy group, an ureide group, and an ammino-base. The number of carbon atoms in the substituent derivative of R1 including the carbon atoms in the substituent group is not greater than eight.
When two R1 groups exist in Formula 1, they may be either identical or different.
The alkyl group of R2 containing 1 to 5 carbon atoms may be, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, and n-pentyl. The acyl group containing 1 to 6 carbon atoms may be, for example, acetyl, propionyl, butyryl, valeryl, and caproyl.
Two or more of the R2 groups in Formula 1 may be either identical or different from each other.
Characteristic examples of the organosilane (1) are tetra-alkoxysilanes including tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane; trialkoxysilane including methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyl-trimethoxysilane, 3- aminopropyltriethoxysilane, 2-hydroxyethyl-trimethoxysilane, 2-hydroxyethyl-triethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyl-trimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl-triethoxysilane, 3-isocianatopropyltrimethoxysilane, 3-isocianatopropyltriethoxysilane, 3-glycidoxypropyl-trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-(meth)-acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyl-triethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, nonafluorohexyl-trimethoxysilane, heptadecafluorodecyltrimethoxysilane, and tridecafluoroctyltrimethoxysilane; dialkoxysilanes including dimethyldirnethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and heptadecafluorodecylmethyldimethoxysilane,; methyltriacetyloxysilane; and dimethyldiacetyloxysilan.
Preferably, it may be selected from trialkoxysilanes and dialkoxysilanes. As for trialkoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, and 3-(meth)acryloxypropyltriethoxysilane are preferred. As for dialkoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane are preferred.
According to the present invention, the organosilane (1) may most preferably be trialkoxysilane or a combination of 40 to 95 mol % of trialkoxysilane and 60 to 5 mol % of dialkoxysilane. The use of dialkoxysilane with trialkoxysilane causes the resultant coating layer to be softened and increased in the resistance to alkalis.
The organosilane (1) may directly be used as a hydrolyzate and/or a condensate. The organosilane (1) employed as the hydrolyzate and/or the condensate enables to be utilized as the component (a) when it has been hydrolyzated and condensed. It is more preferable to perform the hydrolytic and condensing action of the organosilane (1) to yield the component (a) by feeding a proper amount of water during the preparation of the composition as a mixture of the organosilane (1) and the other components, as will explicitly be explained later. The amount of water based on the total amount of a structural unit denoted by (R1)nSiO(4- n)/2 according to the present invention is preferably from 0.5 to 3 moles and more preferably from 0.7 to 2 moles.
When a condensate is used as a component (a), weight-average molecular weight converted as Standard polystyrene (referred to as Mw hereinafter) of the used condensate preferably ranges from 800 to 100,000, more preferably from 1,000 to 50,000.
According to the present invention, the component (a) may be provided as a single substance or a mixture of two or more substances.
The component (a) may either partially or totally include a siloxane oligomer which has SiD bonds and of which the weight-average molecular weight ranges from 300 to 100,000.
The component (a) is commercially available as MKC silicate manufactured by Mitsubishi Chemical Corporation, an ethyl silicate manufactured by Colcoat Co., a silicon resin manufactured by Toray Industries, Inc./Dow-Corning Co., a silicon resin manufactured by Toshiba Silicones Co., a silicon resin manufactured by Shin-Etsu Chemical Co., Ltd., a hydroxyl contained polydimethylsiloxane manufactured by Dow-Corning Asia Co., and a silicon oligomer manufactured by Nippon Unicar Company Limited. In the present invention, those products may be used directly or after subjected to the condensation.
In the present invention, the component (a) may be provided as a single substance or a mixture of two or more substances.
Component (b) (Fluoropolymer Having a silyl Group)
In the invention, component (b) is a fluoropolymer having a structural unit (b-1) and a structural unit (b-2), in which a silyl group having silicon atoms bonded with a hydrolytic group and/or a hydroxy group (referred to as a specific silyl group hereinafter), preferably, is linked to the end and/or side of a molecular chain of the polymer.
The amount of silicon atoms in the component (b) is generally 0.1 to 60 mol % and preferably 0.5 to 50 mol %, based on the total amount of the component (b2).
A preferable form of the specific silyl group is expressed by Formula 4:
(wherein, X is a hydrolytic group or hydroxy groups of halogen atoms, an alkoxy group, an acetoxy group, a phenoxy group, a thioalkoxy group, or an amino group, R6 is hydrogen atoms, an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having 1 to 10 carbon atoms, and i is an integer ranging from 1 to 3).
The component (b) is preferably obtained by polymerizing a monomer (referred to as a monomer (b-1) hereinafter) having the structure unit denoted by Formula 2 and/or a monomer (referred to as a monomer (b-2) hereinafter) having the structural unit denoted by Formula 3 and a monomer (referred to as a monomer (b-3) hereinafter) wherein a set of silicon atoms are bonded to the hydrolytic group and/or the hydroxy group in the specific silyl group and may further be added with another monomer (referred to as a monomer (b-4) hereinafter) which can copolymerize with the foregoing monomers. The monomer (b-4) may contain fluorine atoms which are absent in the other monomers (b-1) and (b-2)
The component (b) may also be a polymer obtained by polymerizing the monomer (b-1) and/or the monomer (b-2); the polymer may be added with the monomer (b-4), if desired, the polymer is modified by reaction with a silane compound (referred to as a silane compound (b-5) hereinafter) which has a functional group capable of reacting with the hydrolytic group or the hydroxy group.
Monomer (b-1)
The monomer (b-1) is expressed by Formula 2xe2x80x2,
(wherein, R3 to R5 are CmY2m+1, m is an integer ranging 0 to 5, and Y is selected from F, H, and Cl separately).
The monomer (b-1) may be a compound having a polymerizable unsaturated double bond and at least one fluorine atom.
More particularly, the monomer (b-1) may be selected from:
(A) fluoroethylenes including CF2xe2x95x90CF2, CHFxe2x95x90CF2, CH2xe2x95x90CF2, CH2xe2x95x90CHF, CClFxe2x95x90CF2, CHClxe2x95x90CF2, CCl2xe2x95x90CF2, CClFxe2x95x90CClF, CHFxe2x95x90CCl2, CH2xe2x95x90CClF, and CCl2xe2x95x90CClF;
(B) fluoropropenes including CF3CFxe2x95x90CF2, CF3CFxe2x95x90CHF, CF3CHxe2x95x90CF2, CF3CFxe2x95x90CH2, CF3CFxe2x95x90CHF, CHF2CFxe2x95x90CHF, CF3CHxe2x95x90CH2, CH3CFxe2x95x90CF2, CH3CHxe2x95x90CF2, CF3CFxe2x95x90CH2, CF2ClCFxe2x95x90CF2, CF3CClxe2x95x90CF2, CF3CFxe2x95x90CFCl, CF2ClCClxe2x95x90CF2, CF2ClCFxe2x95x90CFCl, CF2CCl=CClF, CF2CClxe2x95x90CCl2, CCl3CFxe2x95x90CF2, CF2ClCClxe2x95x90CCl2, CFCl2CClxe2x95x90CCl2, CF3CFxe2x95x90CHCl, CClF2CFxe2x95x90CHCl, CF3CClxe2x95x90CHCl, CHF2CClxe2x95x90CCl2, CF2ClCHxe2x95x90CCl2, CF2ClCClxe2x95x90CHCl, and CCl3CFxe2x95x90CHCl; and
(C) Fluoroolefines having not smaller than four carbon atoms including CF3CF2CFxe2x95x90CF2, CF3CFxe2x95x90CFCF3, CF3CHxe2x95x90CFCF3, CF2xe2x95x90CFCF2CHF2, CF3CF2CFxe2x95x90CH2, CF2CHxe2x95x90CHCF3, CF2xe2x95x90CFCF2CH3, CF2xe2x95x90CFCH2CH3, CF3CH2CHxe2x95x90CH2, CF3CHxe2x95x90CHCH3, CF2xe2x95x90CHCH2CH3, CH3CF2CHxe2x95x90CH2, CFH2CHxe2x95x90CHCFH2, CH3CF2CHxe2x95x90CH2, CH2xe2x95x90CFCH2CH3, CF3(CF2)2CFxe2x95x90CF2, and CF3(CF2)2CFxe2x95x90CF2.
The monomer (b-1) having fluorine atoms may be provided in the form of a single monomer or a combination of two or more monomers.
Monomer (b-2)
The monomer (b-2) is expressed by Formula 3xe2x80x2,
(wherein, Rf is an alkyl group or an alkoxyalkyl group having fluorine atoms and R3 to R5 are analogous to those of Formula 2xe2x80x2 but may be modified without departing from the term of analogy to Formula 2xe2x80x2).
The monomer (b-2) may be a compound having a polymerizable unsaturated double bond, an ether bond, and at least one fluorine atom.
More particularly, the monomer (b-2) may be selected from:
(A) (fluoroalkyl) vinyl ether or (fluoroalkoxyalkyl) vinyl ether expressed by CH2xe2x95x90CHxe2x80x94Oxe2x80x94Rf (wherein, Rf is an alkyl group or an alkoxyalkyl group having fluorine atoms);
(B) perfluoroalkyl vinyl ethers including perfluoromethyl vinyl ether, perfuoroethyl vinyl ether, perfluoroprolyl vinyl ether, perfluorobutyl vinyl ether, and perfluoroisobutyl vinyl ether; and
(C) perfluoroalkoxyalkyl vinyl ethers including perfluoropropoxypropyl vinyl ether.
The monomer (b-2) having fluorine atoms may be provided in the form of a single monomer or a combination of two or more monomers.
When the two monomers (b-1) and (b-2) are used in a combination, they may preferably be hexafluoropropylene and perfluoroalkyl perfluorovinyl ether or perfluoroalkoxyalkyl perfluorovinyl ether.
Monomer (b-3)
The monomer (b-3) is a monomer having a polymerizable unsaturated double bond in one molecule and silicon atoms bonded to a hydrolytic group and/or a hydroxy group.
The monomer (b-3) maybe an unsaturated silane compound expressed by Formula 4xe2x80x2 (referred to as an unsaturated silane compound).
(wherein, X, R6 and i are analogous to those of Formula 4xe2x80x2 and R7 is an organic group having a polymerizable unsaturated double bond).
Characteristic examples of the unsaturated silane compound are:
CH2xe2x95x90CHSi(CH3)(OCH3)2, CH2xe2x95x90CHSi(OCH3)3, CH2xe2x95x90CHSi(OC2H5)3, CH2xe2x95x90CHSi(CH3)Cl2, CH2xe2x95x90CHSiCl3, CH2xe2x95x90CHCOO(CH2)2Si(CH3)(OCH3)2, CH2xe2x95x90CHCOO(CH2)2Si(OCH3)3, CH2xe2x95x90CHCOO(CH2)3Si(CH3)(OCH3)2, CH2xe2x95x90CHCOO(CH2)3Si(OCH3)3, CH2xe2x95x90CHCOO(CH2)2Si(CH3)Cl2, CH2xe2x95x90CHCOO(CH2)2SiCl3, CH2xe2x95x90CHCOO(CH2)3Si(CH3)Cl2, CH2xe2x95x90CHCOO(CH2)3SiCl3, CH2xe2x95x90C(CH3)COO(CH2)2Si(CH3)(OCH3)2, CH2xe2x95x90C(CH3)COO(CH2)2Si(OCH3)3, CH2xe2x95x90C(CH3)COO(CH2)3Si(CH3)(OCH3)2, CH2xe2x95x90C(CH3)COO(CH2)3Si(OCH3)3, CH2xe2x95x90C(CH3)COO(CH2)2Si(CH3)Cl2, CH2xe2x95x90C(CH3)COO(CH2)2SiCl3, CH2xe2x95x90C(CH3)COO(CH2)3Si(CH3)Cl2, and CH2xe2x95x90C(CH3)COO(CH2)3SiCl3,
The compound may be provided in the form of a single compound or a combination of two or more compounds. Monomer (b-4)
The monomer (b-4) capable of copolymerizing with the monomers (b-1) to (b-3) may be selected from:
(A) alkyl (meth)acrylates including methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, amyl (meth)acrylate, i-amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, and cyclohexyl (meth)acrylate;
(B) aromatic vinyl monomers including styrene, xcex1-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, and 1-vinylnaphthalene;
(C) hydroxyalkyl(meth)acrylates including hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyamyl(meth)acrylate, hydroxyhexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and n-octyl(meth)acrylate;
(D) epoxy containing monomers including glycidyl(meth)acrylate, and methylglycidyl(meth)acrylate;
(E) multi-functional monomers including divinylbenzene, ethyleneglycol-di(meth)acrylate, diethyleneglycol-di(meth)acrylate, triethyleneglycoldi(meth)acrylate, tetraethyleneglycol-di(meth)acrylate, propyleneglycol-di(meth)acrylate, dipropyleneglycoldi(meth)acrylate, tripropyleneglycol-di(meth)acrylate, tetrapropyleneglycol-di(meth)acrylate, butanedioldi(meth)acrylate, hexanediol-di(meth)acrylate, trimethylolpropane-tri(meth)acrylate, and pentaerythritol-tetra(meth)acrylate;
(F) acid amide compounds including (meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N,Nxe2x80x2-methylenebisacrylamide, diacetoneacryleamide, maloamide, and maleimide;
(G) vinyl compounds including vinyl chloride, vinylidene chloride, and vinylesters of fatty acids;
(H) aliphatic conjugated dienes including 1,3-butadiene, 2-methyl-1,3-butadinene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadinene, 2-chloro-1,3-butadinene, 2-cyano-1,3-butadinene, isoprene, conjugated pentadiene having straight-chain substituted with a substituent group such as an alkyl group, halogen atoms, or a cyano group, and conjugated hexadinene having straight-chain or side-chain;
(I) ethylene type unsaturated carboxylic acids including (meth) acrylic acid, fuumaric acid, itaconic acid, monoalkyl itaconic acids, maleic acid, crotonic acid, and 2-(meth)acryloyloxyethylhexahydrophthalic acid;
(J) vinyl cyanide compounds including acrylonitrile and methacrylonitrile;
(K) piperidine monomers including 4-(meth)acryloyloxy-2,2,6,6,-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, and 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine;
(L) vinyl ether monomers including vinyl glycidyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinyl ether;
(M) allylethers including allyl glycidyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether
(N) alkyl vinyl ethers and cycloalkyl vinyl ethers including methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether;
(O) fluoro(meth)acrylates including 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl(meth)acrylate, 2-(perfluorobuthyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluorooctyl)ethyl (meth)acrylate, 2-(perfluorodecyl)ethyl (meth)acrylate, 2H,1H,5H-octafluoropentyl(meth)acrylate, and 1H,1H,2H,2H-heptadecafluorodecyl(meth)acrylate;
and other substances including dicaprolactone.
This type of the monomers may be provided in the form of a single monomer or a combination of two or more monomers.
Monomer (b-5) (silane compound)
The silane compound (b-5) used in the addition reaction, for example, halogenated silanes including methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; alkoxysilanes including methyldimethoxysilane, methyldiethoxysilane, phenyldimethoxysilane, trimethoxysilane, and triethoxysilane; acyloxysilanes including methyldiacetoxysilane, phenyldiacetoxysilane, and triacetoxysilane.
These silane compounds may be provided as a single compound or a combination of two or more compounds.
The polymerization of producing the component (b) may be implemented by a process of feeding the monomers at once for polymerization, a process of polymerizing some of the monomers and then continuously or intermittently feeding the remaining monomers, or a process of feeding the monomers in succession throughout polymerization. Also, any combination of the polymerizing processes may be employed. Most preferable is a technique of solution polymerization. The solvent used in the solution polymerization is any commonly available solvent and may preferably be selected from ketones, alcohols, and esters. For the polymerization, a polymerizing initiator, a molecular weight modifier, a chelating agent, and an inorganic electrolyte may be selected from common agents.
The amount of a sum of the structural units (b-1) and (b-2) in the component (b) is generally 0.5 to 80 mol % and preferably 1 to 70 mol %, based on the total amount of the component (b). When the amount is lower than 0.5 mol %, the resultant coating layer may hardly be improved in the transparency and the adhesiveness while repelling water and oils. If higher than 80 mol %, the adhesiveness of the coating layer to a substrate may be declined.
The amount of the structural unit (b-1) is preferably 0.5 to 70 mol %, based on the total amount of the component (b). The amount of the structural unit (b-2) is preferably 0.5 to 70 mol %, based on the total amount of the component (b).
With respect to the amount of the structural unit (b-3), the amount of the specific silyl group is generally 0.1 to 60 mol % and preferably 0.5 to 50 mol %, based on the total amount of the component (b). When the amount is lower than 0.1 mol %, the effect of condensation together with the component (a) will hardly be ensured. If higher than 60 mol %, the storage stability of the resultant coating composition will be declined.
The amount of the structural unit (b-4) composed of the monomer (b2-4) capable of copolymerizing with the other monomers is generally not higher than 90 mol % and preferably not higher than 80 mol %, based on the total amount of the component (b).
Mw of the component (b) is preferably 1,000 to 50,000 and more preferably 5,000 to 30,000.
In the invention, the component (b) may be provided in the form of a single substance or a combination of two or more substance as described above.
The amount of the component (b) in the coating composition is generally 20 to 500 weight parts, preferably 25 to 400 weight parts, and more preferably 50 to 300 weight parts, based on 100 weight parts of the structural unit (R1)nSiO(4-n)/2 in the component (a). When the amount of component (b) is smaller than 20 weight parts, the resultant coating layer will be declined in the resistance to alkalis and cracking. If greater than 500 weight parts, the resistance to weather of the coating layer will be declined.
In the present invention, a vinyl copolymer having the specific silyl group and having no fluorine atoms (referred to as component (bxe2x80x2) hereinafter) may be used in addition to the component (b) without impairing the effect of the invention. The component (bxe2x80x2) is provided by copolymerization of the foregoing monomers (b-3) and (b-4) or addition reaction of a polymer obtained from the monomer (b-4) with a silane compound (b-5). In the coating composition of the invention, the amount of the component (bxe2x80x2) is generally not greater than 500 weight parts, based on 100 weight parts of the structural unit (R1)nSiO(4-n)/2 of the component (a).
According to the present invention, an organic solvent is used to obtain a uniform mixture of the component (a), the component (c), and the other relevant components (c) to (e), and to have a desired concentration of all solids in the composition. In addition, the organic solvent may assist each of a variety of coating processes and thus increase the dispersion stability and the storage stability of a resultant coating composition.
The organic solvent used for mixing up the components uniformly is of no limitations and may be selected from, for example, alcohols, aromatic hydrocarbons, ethers, ketones, and esters.
The alcohols for the organic solvent include specifically methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, and diacetone alcohol.
The aromatic hydrocarbons include specifically benzene, toluene, and xylene. The ethers include specifically tetrahydrofuran and 1,4-dioxane. The ketones include specifically acetone, methyl ethyl ketone, methyl isobutyl ketone, and di-isobutyl ketone. The esters include specifically ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
The organic solvent may be provided as a single solvent or a combination of two or more solvents.
While coating composition of the invention is able to provide a coating layer improved in the resistance to fouling derived from water and oil repellency, it is favorable to form a undercoating layer on the substrate surface in order to impart the functions of the long-term adhesiveness and shield from ultraviolet ray. Preferable examples of the undercoating composition for a undercoating layer are the compositions (i) and (ii). The composition (i) is more preferable.
The undercoating compositions (i) and (ii) will be explained in detail below.
The undercoating composition (i) contains the above component (a). For preparing the composition (i), water is added to carry out the hydrolysis and condensation of the organosilane (1) preferably. Further, hydrolyzates and/or condensates of the organosilane (1) can be used as component (a).
The undercoating composition (ii) contains the above component (a) and silyl group having polymer (bxe2x80x2). Componet (bxe2x80x2) (silyl group having polymer)
The component (bxe2x80x2) is a polymer in which no fluorine is contained and a silyl group is linked to the end and/or side of a molecular chain of the polymer. The component (bxe2x80x2) in the composition (ii) allows the hydrolytic and/or hydroxy groups in its specific silyl group to be condensed together with the component (a) thus contributing to the improvement in the coating layer characteristics.
The amount of silicon in the component (bxe2x80x2) is generally 0.001 to 20 percent by weight and preferably 0.01 to 15 percent by weight, based on the total amount of the component (bxe2x80x2).
A preferable form of the specific silyl group is expressed by above Formula 4.
The component (bxe2x80x2) (silyl group having polymer) is provided by the method of producing the component (b) (fluoropolymer having a silyl group) while using at least one kind of monomers lacking in fluorine selected from the monomers showed as monomer (b-4) in place of monomers (b-1) and (b-2).
Alternatively, the component (bxe2x80x2) may be selected from epoxy resins containing the specific silyl group and polyester resins containing the specific silyl group.
The epoxy resin containing the specific silyl group may be produced by causing the epoxy group in an epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic poly(glycidyl ether), or aliphatic poly(glycidyl ester) to react with aminosilanes, vinylsilanes, carboxysilanes, or glycidylsilanes having the specific silyl group.
The polyester resin containing the specific silyl group may be produced by causing the carboxyl group or hydroxy group in a polyester resin to react with aminosilanes, carboxysilanes, or glycidylsilanes having the specific silyl group.
Mw of the component (bxe2x80x2) ranges preferably 2,000 to 100,000 and more preferably 4,000 to 50,000.
The amount of the component (bxe2x80x2) used in the composition (ii) is generally 2 to 900 weight parts, preferably 10 to 850 weight parts, and more preferably 20 to 800 weight parts, based on 100 weight parts of the structural unit (R1)nSiO(4-n)/2 in the component (a). In that case, when the amount of component (bxe2x80x2) is smaller than 2 weight parts, its resultant coating layer will be declined in the resistance to alkalis. If higher than 900 weight parts, the resistance to weather of the coating layer throughout a long period of time will be lowered.
According to the invention, the component (bxe2x80x2) may be provided in the form of a single substance or a combination of two or more substance as described above.
Preferably, the component (b) in the composition (ii) may be condensed together with the component (a) under the presence of water and/or an organic solvent.
The kind and the amount of component (a) in composition (ii) is the same as the above coating composition.
Each of the coating composition of the invention and compositions (i) and (ii) may further be added with the following components (c) to (e) as well as other additives, which will be explained below.
The component (c) is a catalyst for encouraging the hydrolysis and condensation of the components (a), (b) and (bxe2x80x2).
The use of the component (c) will accelerate the speed of curing the resultant coating layer and increase the molecular weight of polysiloxane produced by poly condensation of the organosilane component, hence allowing the resultant coating layer to be improved in the physical strength and the long-term durability as well as making the coating layer thickness increased and facilitating the coating application.
The component (c) is preferably selected from acidic compounds, basic compounds, metallic salts, amine compounds, and organometallic compounds and/or their partial hydrolyzates (the organometallic compounds and/or their partial hydrolyzates being referred to as organometallic compounds).
Characteristic examples of the acidic compound are acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyltitanic acid, p-toluenesulphonic acid, and phthalic acid and it may preferably be acetic acid.
Characteristic examples of the basic compound are sodium hydroxide and potassium hydroxide and it may preferably be sodium hydroxide.
Characteristic examples of the metallic salts are alkali metallic salts of naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminic acid and carbonic acid.
Characteristic examples of the amine compound are ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperadine, m-phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)-aminopropyltrimethoxysilane, 3-(2-aminoethyl)-aminopropyltriethoxysilane, 3-(2-aminoethyl)-aminopropylmethyldimethoxysilane, 3-anilinopropyltrimethoxysilane, alkylamine salts, quaternary ammonium salts, and modified amines used as a hardener for epoxy resin, and preferably it may be 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, or 3-(2-aminoethyl)-aminopropyltrimethoxysilane.
The organometallic compound may be selected from a particular compound expressed by Formula 5 shown below (referred to as anorganometallic compound (5) hereinafter), an organometallic compound of tetravalent tin having 1 to 2 alkyl groups where 1 to 10 carbon atoms are bonded to the corresponding number of tin atoms (referred to as an organic tin compound hereinafter), and their hydrolyzates.
M(OR8)p(R9COCHCOR10)qxe2x80x83xe2x80x83(5)
(wherein, M is zirconium, titanium, or aluminum, R8 and R9, different or identical to each other, are monovalent hydrocarbon groups having 1 to 6 carbon atoms such as ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, or phenyl, R10 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, like R8 or R9, or an alkoxyl group having 1 to 16 carbon atoms such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, lauryloxy, or stearyloxy, and p and q are integers ranging from 0 to 4, (p+q)=(valence of M).)
The organometallic compound (5) may be selected from:
(A) organic zirconium compounds including zirconium tetra-n-butoxide, zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxy-bis(ethylacetoacetate), zirconium n-butoxy-tris(ethylacetoacetate), zirconium tetrakis(n-propylacetoacetate), zirconium tetrakis(acetylacetoacetate), and zirconium tetrakis(ethylacetoacetate);
(B) organic titanium compounds including titanium tetra-i-propoxide, titanium di-i-propoxy bis(ethylacetoacetate), titanium di-i-propoxy bis (acetylacetate), and titanium di-i-propoxy bis(acetylacetone); and
(C) organic aluminum compounds including aluminum tri-i-propoxide, aluminum di-i-propoxy ethylacetoacetate, aluminum di-i-propoxy acetylacetonate, aluminum i-propoxy bis(ethylacetoacetate), aluminum 1-propoxy bis(acetylacetonate), aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and aluminum monoacetylacetonate-bis(ethylacetoacetate).
The organometallic compound (5) and its partial hydrolyzate may preferably be selected from zirconium tri-n-butoxy-ethylacetoacetate, titanium di-i-propoxy bis(acetylacetonate), aluminum di-i-propoxy ethylacetoacetate, aluminum tris (ethylacetoacetate), and their partial hydolyzates.
The organic tin compound may be selected from:
carbonic acid organic tin compounds including (C4H9)2Sn(OCOC11H23)2, (C4H9)2Sn(OCOCHxe2x95x90CHCOOCH3)2, (C4H9)2Sn(OCOCHxe2x95x90CHCOOC4H9)2, (C8H17)2Sn(OCOC8H17)2, (C8H17)2Sn(OCOC11H23)2, (C8H17)2Sn(OCOCHxe2x95x90CHCOOCH3)2, (C8H17)2Sn(OCOCHxe2x95x90CHCOOC4H9)2, (C8H17)2Sn(OCOCHxe2x95x90CHCOOC8H17)2, (C8H17)2Sn(OCOCHxe2x95x90CHCOOC16H33)2, (C8H17)2Sn(OCOCHxe2x95x90CHCOOC17H35)2, (C8H17)2Sn(OCOCHxe2x95x90CHCOOC18H37)2, (C8H17)2Sn(OCOCHxe2x95x90CHCOOC20H41)2,
(C4H9)Sn(OCOC11H23)3, and (C4H9)Sn(OCONa)3;
mercaptide organic tin compounds including
(C4H9)2Sn(SCH2COOC8H17)2, (C4H9)2Sn(SCH2CH2COOC8H17)2, (C8H17)2Sn(SCH2COOC8H17)2, (C8H17)2Sn(SCH2CH2COOC8H17)2, (C8H17)2Sn(SCH2COOC12H25)2, (C8H17)2Sn(SCH2CH2COOC12H25)2, (C4H9)Sn(SCOCHxe2x95x90CHCOOC8H17)3, (C8H17)Sn(SCOCHxe2x95x90CHCOOC8H17)3,
sulfide organic tin compounds including (C4H9)Snxe2x95x90S, (C8H17)2Snxe2x95x90S, and
chloride organic compounds including (C4H9)SnCl3,
(C4H9)2SnCl2, (C8H17)2SnCl2, and
organic tin oxides including (C4H9)2SnO and (C8H17)2SnO as well as reaction products produced by the reaction between these organic tin oxide and an ester compound such as ethyl silicate, dimethyl maleate, diethyl maleate, or dioctyl phthalate.
The component (c) maybe provided in the form of a single substance or a combination of two or more substances and may be mixed with a zinc compound or a reaction retardant.
The component (c) may also be fed at a stage for preparation of the composition or at a stage where a coating layer is formed or at both the stages for preparation of the composition and for forming the coating layer.
The amount of the component (c), except the organometallic compounds, based on 100 weight parts of the structural unit, (R1)nSiO(4-n)/2, in the component (a) is generally 0 to 100 weight parts, preferably 0.01 to 80 weight parts, and more preferably 0.1 to 50 weight parts. The amount of the component (c) of any organometallic compound based on 100 weight parts of the structural unit, (R1)nSiO(4-n)/2, in the component (a) is generally 0 to 100 weight parts, preferably 0.1 to 80 weight parts, and more preferably 0.5 to 50 weight parts. When the amount of the component (c) exceeds 100 weight parts, the composition will be declined in the storage stability and its resultant coating layer will suffer from cracking.
The component (d) may be at least one expressed by Formula 6 and selected from xcex2-diketones, xcex2-ketoesters, carbonic acid compounds, compounds having two hydroxy groups, amine compounds, and oxyaldehydes.
R9COCH2COR10xe2x80x83xe2x80x83(6)
(wherein, R9 and R10 are analogous to those in Formula 5).
The component (d) is preferably added when an organometallic compound is used as component (c).
The component (d) serves as a stability enhancing agent for the composition. More specifically, it is presumed that the component (d) is coordinates bonded to metallic atoms in the organometallic compound thus to appropriately control the promotion of co-condensation of the components (a), (b), and (bxe2x80x2) with the organometallic compound, hence improving the storage stability of the composition.
Characteristic examples of the component (d) are acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate, hexane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5-methylhexane-2,4-dione, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, amino acetic acid, imino acetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,2-bipyridine, 1,10-phenanthroline, diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithizone, methionine, and salicylaldehyde. It may preferably be acetylacetone or ethyl acetoacetate.
The component (d) maybe provided in the form of a single substance or a combination of two or more substances.
The amount of the component (d) based on 1 mole of the organometallic compound is generally not smaller than 2 moles and preferably 3 to 20 moles. When the amount of the component (d) is smaller than 2 moles, improvement in the storage stability of the resultant composition will be uncertain.
The component (e) is a powder and/or a sol or a colloid form of an inorganic compound having no photocatalytic function and may be fed so that the resultant coating layer has desired properties.
Characteristic examples of the component (e) are SiO2, Al2O3, AlGaAs, Al (OH)3, Sb2O5, Si3N4, SnO2, Snxe2x80x94In2O3, In2O3, Sbxe2x80x94In2O3, InSb, InAs, InGaAlP, MgF, CeF3, CeO2, 3Al2O3xe2x80x942SiO2, BeO, SiC, AlN, Fe, Fe2O3, Co, Coxe2x80x94FeOx, CrO2, Fe4N, BaTiO3, BaOxe2x80x94Al2O3xe2x80x94SiO2, Ba ferrite, SmCO5, YCO5, CeCO5, PrCO5, Sm2CO17, Nd2Fe14B, ZnO2, Al4O3, AlN, SiC, xcex1-Si, SiN4, CoO, Sb2O5, MnO2, MnB, Co3O4, Co3B, LiTaO3, MgO, MgAl2O4, BeAl2O4, ZrSiO4, ZnO, ZnS, ZnSe, ZnSb, ZnTe, PbTe, PbS, PbSe, GeSi, FeSi2, CrSi2, CoSi2, MnSi1.73, Mg2Si, xcex2-B, BaC, BP, TiB2, ZrB2, HfB2, Ru2Si3, RuO2, TiO2, TiO3, SrTiO3, FeTiO3, PbTiO3, Al2TiO5, Zn2SiO4, Zr2SiO4, 2MgO2xe2x80x94Al2O3xe2x80x945SiO2, WO3, Bi2O3, CdO, CdS, CdSe, GaP, GaAs, CdFeO3, MoS2, LaRhO3, GaN, CdP.,Nb2O5, GaAsP, Li2Oxe2x80x94Al2O3xe2x80x944SiO2, Mg ferrite, Ni ferrite, Nixe2x80x94Zn ferrite, Li ferrite, and Sr ferrite.
The component (e) may be provided in the form of a single substance or a combination of two or more substances.
The colloidal silica form of the component (e) may commercially be available as, for example, Snowtex, Isopropanol Silicasol, and Methanol Silicasol by Nissan Chemical Industries, Ltd; Cataloid and Oscar by Catalysts and Chemicals Industries Co., LTD; Ludox by Du pont, U.S.A.; Syton by Monsanto, U.S.A., and Nalcoag by Nalco Chemical, U.S.A. The colloidal alumina form of the component (e) may be available asAlminasol-100, and Aluminasol-520 by Nissan Chemical Industries, Ltd.
In order to impart photocatalytic function, the component (e) may include TiO2 (preferably Anatase type). The component (e) may also include CeO2 or ZnO which acts as an ultraviolet ray absorber.
The average particle diameter of the component (e) is preferably 30 xcexcm or less, more preferably 0.005 to 20 xcexcm, most preferably 0.005 to 10 xcexcm. If the average particle diameter is more than 30 xcexcm, the smoothness of the surface of the coating is not achieved.
The component (e) may also be provided in a powder form, an aqueous sol or colloidal form where the substance is dispersed in water, or a solvent sol or colloidal form where the substance is dispersed in a polar solvent such as isopropyl alcohol or a less-polar solvent such as toluene. The component (e) of the solvent sol or colloidal form may further be diluted with water or the solvent depending on the dispersing properties of the component (e) or may be surface-treated for improving the dispersing properties.
When the component (e) is the aqueous sol or colloidal form, its solid concentration may preferably be not greater than 40 percent by weight.
The method of combining the component (e) with the composition may involve feeding the component (e) after the preparation of the composition or feeding the same during the preparation of the composition to allows the hydrolysis and co-condensation with the components (a), (b), and (bxe2x80x2) or their condensates.
The amount of the component (e) based on 100 weight parts of the structural unit, (R1)nSiO(4xe2x88x92n)/2, in the component (a) is generally 0 to 500 weight parts and preferably 0.1 to 400 weight parts in solid state.
The coating composition of the present invention may be added with the optional components described later.
The coating composition may include an organic ultraviolet ray absorber and a stabilizer. Specific examples of the organic ultraviolet ray absorber are benzophenones, benzotriasols, triadines, and phenols. And specific examples of the stabilizer are hindered amines. These additives may be provided in the form of a single substance or structural unit of a copolymer.
The composition of the present invention may have an appropriate filler added and dispersed for improving the color and the thickness of a resultant coating layer.
The filler may be selected from non-aqueous organic pigments, non-aqueous inorganic pigments, ceramics, metals, and alloys of a particle, fiber, or scale form, and their oxides, hydroxides, carbides, nitrides, and sulfides.
Characteristic examples of the filler are iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium dioxide for pigment, aluminum oxide, chrome oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatom earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, viridian, Guignet""s green, cobalt chrome green, shale green, green soil, manganese green, pigment green, ultramarine, deep blue, pigment blue, rockyblue, cobalt blue, cerulean blue, copper borate, molybdenum blue, copper sulfide, cobalt purple, mars violet, manganese purple, pigment violet, lead suboxide, calciumhydrochloride, zinc yellow, lead sulfide, chrome yellow, yellow soil, cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, copper suboxide, cadmium red, selenium red, chrome vermilion, Indian red, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zirconium oxide, tungsten white, lead, zinc white, Bantison white, lead phthalate, manganese white, lead sulfate, carbon black, bone black, diamond black, Thermatomic black, plant black, potassium titanate whisker, and molybdenum disulfide.
The filler may be provided in the form of a single substance or a combination of two or more substances.
The amount of the filler based on 100 weight parts of the solids of the composition is generally not greater than 300 weight parts.
Other particular agents to be added to the composition of the present invention, if desired, are known dehydrating agents including methyl orthoformate, methyl orthoacetate, and tetraethoxysilane; dispersing agents including poly(oxyethylene alkyl ether), poly(oxyethylene alkyl phenyl ether), poly(oxyethylene ester of fatty aid), poly(carbonic acid) polymer surfactant, polycarboxylate, polyphosphate, polyacrylate, polyamide ester salt, and polyethylene glycol; thickening agents including cellulose such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, or hydroxypropylmethyl cellulose, castor oil derivative, and ferrosilicate; inorganic foaming agents including ammonium carbonate, ammonium bicarbonate, ammonium subnitrate, sodium boron hydride, and calcium azide; organic foaming agents including an azo compound such as azobisisobutyronitrile, a hydrazine compound such as diphenylsulfone-3,3xe2x80x2-disulfohydrazine, a semicarbazide compound, a triazole compound, and an N-nitroso compound; and other additives including a surfactant, a silane coupling agent, a titanium coupling agent, and a dye.
Also, a leveling agent may be combined for improving the coating performance of the composition. The leveling agent may commercially be available: as a fluorine leveling agent, BM1000 and BM1100 by BM-Chemie, Efca 772 and Efca 777 by Efca Chemicals, a Florence series by Kyoeisha Chemical, an FC series by SUMITOMO 3M LIMITED, and a Fluonal TF series by Toho Chemical; as a silicone leveling agent, a BYK series by BYK Chemie, a Sshmego series by Sshmegmann, and Efca 30, Efca 31, Efca 34, Efca 35, Efca 36, Efca 39, Efca 83, Efca 86, and Efca 88 by Efca Chemicals; and as an ether or ester leveling agent, Carphynol by Nisshin Chemical and Emargen and Homogenol by Kao Corporation.
The use of the leveling agent will improve the appearance of a finished coating layer and also allow the coating layers to be coated uniformly as a thin film.
The amount of the leveling agent to be used, based on the entirety of the component, is preferably 0.01 to 5 percent by weight and more preferably 0.02 to 3 percent by weight.
Further, the composition of the invention may have a fungus resistance agent corresponding to the purpose of application. The fungus resistance agent may be selected from;
(A) metal ion carrying inorganic fungus resistance agents having carrier such as synthetic zeolite, calcium phosphate, zirconium phosphate, vanadium phosphate, calcium silicate, silicagel, amino acids, metal soaps, ceramics, apatite, activated carbon, montmorinite and depolymerized glass, and metals such as silver, copper, and zinc, and
(B) organic fungus resistance agents such as phenol ethers, sulfons, imidazols, oxybisphenoxyarsine, organic nitrosulfuric compounds, nitrile compounds, benzothiazole compounds, isothiazole compounds, thiadiazole compounds, triazine compounds, pyrrole compounds, and aliphatic imido compounds.
The composition of the present invention or more particularly, the compositions (i) or (ii) for undercoating may be blended with another resin. Characteristic examples of the another resin are acrylic-urethane resin, epoxy resin, polyester, acrylic resin, fluorine resin, acrylic resin emulsion, epoxy resin emulsion, urethane emulsion, and polyester emulsion.
The composition of the present invention which does not include the component (bxe2x80x2), or the composition (ii) maybe blended with the component (bxe2x80x2), water and/or organic solvent. In this case, the amount of the additional component (bxe2x80x2) is the same as above.
The preparation of the coating composition and undercoating composition of the present invention is not limited to a specific mixing method when the two components (c) and (d) are unused. In case that the components (c) and (d) are used, a process may preferably be employed of preparing a mixture of the components (a) to (e) excluding the component (d) and then doping the component (d) into the mixture.
The coating composition of the invention may be produced by the following methods (1) to (4).
(1): A method of adding a specific amount of water to the mixture including organosilane (1) (component (a)), component (b), component (c), and the desired amount of an organic solvent resulting in hydrolyzation and condensation, followed by adding component (d) therein.
(2): A method of adding a specific amount of water to the mixture including organosilane (1) (component (a)) and the desired amount of an organic solvent resulting in hydrolyzation and condensation, followed by adding component (b) and component (c) resulting in condensation, adding component (d) thereafter.
(3): A method of adding a specific amount of water to the mixture including organosilane (1) (component (a)), component (c) and the desired amount of an organic solvent resulting in hydrolyzation and condensation, followed by adding component (b) resulting in partially condensation, adding component (d) thereafter.
(4): A method of adding a specific amount of water to the mixture including, a portion of organosilane (1) (component (a)), component (b), component (c) and the desired amount of an organic solvent, resulting in hydrolyzation and condensation, followed by adding the rest of organosilane (1) resulting in hydrolyzation and condensation, adding component (d) thereafter.
In the present invention, optional components except components (a) to (d) may be added at an appropriate step in preparing the coating composition of the invention.
The concentration of all solids in the coating composition of the present invention is generally 1 to 45 percent by weight, preferably 2 to 40 percent by weight. The solid concentration may be adjusted corresponding to the purpose of application. When the solid concentration in the composition exceeds 45 percent by weight, the storage stability will be declined.
The concentration of all solids in the undercoating composition (i) or (ii) of the present invention is generally not higher than 50 percent by weight, preferably not higher than 40 percent by weight. The solid concentration may be adjusted depending on the type of a substrate, the method of coating, the thickness of a coating layer, and so forth.
Coated Film
The coated film of the present invention consists mainly of a substrate (film)/an undercoating composition (i) or (ii)/a coating composition, or a substrate/a primer/an undercoating composition (i) or (ii)/a coating composition.
The application of any of the compositions of the invention may be conducted by a known manner such as dip coating, flow coating, spraying, screening, electric deposition, vapor deposition, using a brush, a roll coater, a flow coater, a centrifugal coater, an ultrasonic coater, or a (micro) gravure coater.
In forming a layer of the coating composition of the invention on a substrate, the thickness of a coating layer is substantially 0.05 to 20 xcexcm (dried) with single coating application and 0.1 to 40 xcexcm with two times coating application. After dried at an ordinary temperature or heated to 30 to 200xc2x0 C. commonly for 1 to 60 minutes, the coating layer will set on the substrate of a desired type.
In application of the undercoating composition (i) or (ii), the thickness of a undercoating layer is substantially 0.05 to 20 xcexcm (dried), with single undercoating application and 0.1 to 40 xcexcm with two times undercoating application. After dried at an ordinary temperature or heated to 30 to 200xc2x0 C. commonly for 1 to 60 minutes, the undercoating layer will set on the substrate of a desired type.
The total thickness of the undercoating and the overcoating layers may normally be 0.1 to 80 xcexcm and preferably 0.2 to 60 xcexcm after drying.
Corresponding to the use, a primer may also be used in the invention. The primer is not limited to a specific type and may be selected from a variety of materials which enable to enhance the bonding between the substrate and the composition, according to the type of the substrate and the purpose of use. The primer may also be provided in the form of a single substance or a combination of two or more substances. The primer may be an enamel containing a coloring material such as a pigment or may have transparency without such a coloring material.
Characteristic examples of the primer are alkyd resin, aminoalkyd resin, epoxy resin, polyester, acrylic resin, urethane resin, fluorine resin, acrylsilicone resin, acrylic resin emulsion, epoxy resin emulsion, polyurethane emulsion, and polyester emulsion. The primer may have various functional radicals when a higher degree of adhesiveness is required between the film substrate and the coating layer in hostile conditions. The functional radicals include, for example, a hydroxy group, a carboxyl group, an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an ether bond, and an ester bond. The primer may also contain an ultraviolet light absorber, an ultraviolet light stabilizer, and so forth.
For increasing the abrasion resistance and the glossiness of the coating layer of the invention, the coating layer may be protected at the upper surface with a clear layer composed of, for example, a siloxane resin paint which may be a stable dispersion of colloidal silica and siloxane resin such as disclosed in U.S. Pat. Nos. 3,986,997 and 4,027,073.
The substrate film which is able to associate with the composition of the present invention is provided as an organic film selected from polyesters including poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), and poly(ethylene-2.6-naphthalate) (PEN); polyamides including nylon 6 and nylon 6,6; polyolefins including polyethylene (PE) and polypropylene (PP); polyacryls including polycarbonates (PC) and poly(methacrylate methyl) (PMMA); and ABS resins. The organic film may be a fluorine film such as poly(tetrafluoroethylene) (PTFE) or ethylene-tetrafluoroethylene (ETFE).
The substrate may preliminarily be surface treated for base preparation, improvement in adhesiveness, sealing of porous materials, smoothing, and particular decoration.
Characteristic examples of the surface treatment are blasting, chemical treatment such as alkali treatment, degreasing by a solvent, flaming, oxidation treatment, vapor treatment, corona discharge treatment, UV ozone treatment, ultraviolet radiation, plasma treatment, ion treatment and so forth.
Coated Glass
The coated glass of the present invention consists mainly of a substrate/an undercoating composition (i) or (ii)/a coating composition, or a substrate/a primer/an undercoating composition (i) or (ii)/a coating composition. The application of any of the compositions of the invention may be conducted by the same manner as above coated films.
Substrate Glass
The substrate glass which is able to associate with the composition of the present invention is provided as an inorganic glass such as a clear glass, a green glass, a bronze glass, a tempered glass, a partially tempered glass, a laminated glass, and a glass coated with an ITO conductive film.
The substrate may preliminarily be surface treated for base preparation, improvement in adhesiveness, sealing of porous materials, smoothing, and particular decoration.
The substrate glass of the present invention can be used such as a house window, a front and rear automobile window, a varieties of windows used in a vehicle such as a train, an airplane, a boat, a ship, a top-covered motorcycle, a submarine, a spaceship, a roller coaster, a Ferris wheel; a side and inner mirror of an automobile, a traffic safety mirror set up on the road side, a protection glass used in a device of the generation of electricity such as a protection sheet for a solar cell, a glass used in a monitor, a looking glass, a glass door, and a glass part of a furniture.
With respect to the inorganic glass substrate, characteristic examples of the surface treatment are rubbing, degreasing, metal plating, acid treatment, chroming, flaming, coupling treatment, UV ozone treatment, and so forth.
As set forth above, the coating composition of the present invention enable to provide a coated film and coated glass improved in the resistance to fouling derived from water and oil repellency without declining the adhesiveness, the resistance to weather, heat, alkalis, organic chemicals, moisture, and (hot) water.
The embodiment of the present invention will be described in more detail referring to some examples. It would be understood that the present invention is not limited to the following examples.
The amounts in the examples and their relevant =preparations are denoted in the unit of parts or percent on a weight basis, unless otherwise specified. The measurement and estimation of each characteristic factor was carried out by the following manners.
(1) Mw
A gel permeation chromatography (GPC) method was used under the following conditions.
Test sample: Tetrahydrofuran was used as a solvent. 1 g of a partial condensate of organosilane or 0.1 g of a silyl contained vinyl resin was dissolved in 100 cc of the tetrahydrofran to prepare a test sample. Standard polystyrene: Standard polystyrene made by Pressure Chemical, U.S.A.
Apparatus: A high-temperature, high-speed gel permeation chromatogram (a model, 150-C ALC/GPC) by Waters, U.S.A.
Column: A model, Shodex A-80M (length 50 cm) by SHOW A DENKO K.K., Japan.
Measurement temperature: 40xc2x0 C.
Flow rate: 1 cc/min.
(2) Storage Stability
The coating composition containing no curing accelerator is stored in a bottle of polyethylene at room temperature for 3 months. Then gelation of the coating composition is examined by visual inspection. Viscosity of the composition showing no gelation is measured by BM type viscometer (manufactured by Tokyo Keiki Co. Ltd.). The composition exhibiting a change in a rate of viscosity not more than 20 percent based on that of the initial composition was classified as xe2x80x9cgoodxe2x80x9d.
(3) Adhesiveness
A tape peeling test was conducted three times using a matrix (of 100) specified in JIS K5400 and its average was measured.
(4) Hardness
This measurement was based on a pencil hardness specified by JIS K5400.
(5) Resistance to Alkalis
After a coating test piece was immersed in a saturated calcium hydroxide solution for 60 days, its coating layers were examined visually. The test piece exhibiting no change was classified as xe2x80x9cgoodxe2x80x9d.
(6) Resistance to Organic Chemicals
The coating test piece was applied with 2 cc of isopropyl alcohol, and wiped off after 5 minutes. Then, the test piece was visually examined. The test piece exhibiting no change was classified as xe2x80x9cgoodxe2x80x9d.
(7) Resistance to Moisture
After a test piece was left at a temperature of 50xc2x0 C. and a moisture of 95 RH % for 1,000 hours continuously, its coating layers were visually examined. The test piece exhibiting no change was classified as xe2x80x9cgoodxe2x80x9d.
(8) Resistance to Weather
A 3,000 hours irradiation test with a Sunshine weather meter made by Suga Test was carried out according to JIS K5400 and the coating layers of a test piece were visually examined for the state of appearance (cracking and peeling) The test piece exhibiting no change was classified as xe2x80x9cgoodxe2x80x9d.
(9) Resistance to Water
After a test piece was immersed in tap water at room temperature for 60 days, the coating layer of a test piece were visually examined for the state of appearance (cracking and peeling). The test piece exhibiting no change was classified as xe2x80x9cgoodxe2x80x9d.
(10) Resistance to Hot Water
After a test piece was immersed in hot water at 60xc2x0 C. for 14 days, the coating layers of a test piece were visually examined for the state of appearance (cracking and peeling) The test piece exhibiting no change was classified as xe2x80x9cgoodxe2x80x9d.
(11) Resistance to Fouling
After the coating layer of a test piece were fouled with a mixture paste of carbon black/kerosine oil=1/2 (in weight ratio), left at room temperatures for 24 hours, and rinsed with water using a sponge, the test piece was visually examined. The evaluation was based on the following criteria.
∘: Not fouled.
xcex94: Slightly fouled.
xc3x97: Terribly fouled.
(12) Transparency
The coating composition is coated on quartz glass obtaining a 10 xcexcm thickness (dried) of the coating layer. The transparency of visible radiation of the coating layer is measured. The evaluation was based on the following criteria.
⊚: Transparency higher than 80%.
∘: Transparency between 60 and 80%.
xcex94: Transparency smaller than 60%.
(13) Water and Oil Repellency
A slope angle is measured, at which one drop of water or salad oil (manufactured by THE NISSHIN OIL MILLS, LTD.) on the surface of the above obtained coating layer slips down. The evaluation was based on the following criteria.
∘: slope angle smaller than 60xc2x0.
xcex94: slope angle between 60 and 90xc2x0.
xc3x97: no slip down at a slope angle of 90xc2x0.
(14) Contact Angle
A contact angle of 3 xcexcl of pure water or coal tar (industrial coal tar according to JIS K2439) on the above obtained coating layer is measured by an auto-contact angle meter manufactured by Kyowa Kaimen Kagaku Ltd.
(15) Abrasion Resistance
The coating layer is examined by a taper type abrasion testing machine using abrasion ring of cs-10 at a weight of 0.5 kg and at 500 rotation. The difference between the haze of coating layer before test and that of coating layer after test is examined. The evaluation was based on the following criteria.
∘: difference smaller than 1.
xcex94: difference equal to or smaller than 5.
X: difference greater than 5.
(16) Exfoliation of Stacked Outer Layer
The above coated film is further coated by bisphenol A type epoxy resin to form an outer layer of a thickness of 50 xcexcm. A exfoliation test (of 180xc2x0) is conducted according to JIS K6854-3. The evaluation was based on the following criteria.
∘: the outer layer is released completely.
xcex94: the outer layer is released partially.
xc3x97: the outer layer is not released.
Preparation 1 (of the Component (b))
A stainless autoclave equipped with an electromagnetic stirrer was subjected to substitution with a nitrogen gas and filled with 150 parts of methyl isobutyl ketone, 30 parts of ethyl vinyl ether, and 2 parts of lauroyl peroxide (a radical polymerization initiator). The reaction mixture was cooled down to xe2x88x9250xc2x0 C., and then deoxygenated using nitrogen gas. Then, 65 parts of hexafluoropropylene and 5 parts of vinyltrimethoxysilane was added to the reaction mixture and it was heated up. When the temperature in the autoclave was increased up to 60xc2x0 C., the interior pressure was 5 kgf/cm2.
The mixture was stirred for 20 hours at 60xc2x0 C. to complete the polymerization reaction. When the pressure in the autoclave dropped down to 1.5 kgf/cm2, the mixture was cooled down with water to quench the reaction. The total solid content of the polymer solution was 40% (referred to as (B-1)).
Preparations 2 to 5 (of the Component b).
By the same manner as of Provision 1 except for the monomers used as shown in Table 1, polymer solutions (B-2 to B-5) having a solid concentration of 40% were prepared.
Preparation 6 (of the Component (bxe2x80x2)(Silyl Group Having Polymer))
In a reactor equipped with a circulating cooler and a stirrer, 70 parts of methyl methacrylate, 40 parts of n-butyl acrylate, 20 parts of xcex3-methacryloxypropyltrimethoxysilane, 7 parts of acrylic acid, 13 parts of 2-hydroxyethyl methacrylate, 150 parts of i-propyl alcohol, 50 parts of methyl ethyl ketone, and 25 parts of methanol were mixed up. The mixture was then heated to 80xc2x0 C. while being stirred and 4 parts of azobisisovaleronitrile dissolved into 10 parts of xylene was added gradually for 30 minutes. After the reaction mixture was kept at 80xc2x0 C. for 5 hours, a polymer solution (referred to as (bxe2x80x2-1) hereinafter) having a solid concentration of 40% was obtained.

Coating composition, and a coated film and glass each having a coating layer comprised thereof


A multi-channel communication circuit includes a master device, a plurality of slave devices, and a multiplexer (MUX). A transmitting pin and a receiving pin of a serial interface of the master device are respectively connected to a first data input pin and a first data output pin of the MUX. Two control pins of the serial interface of the master device are connected to two selecting pins of the MUX. Four pins of the serial interface of the master device are connected to a power pin of the MUX. Transmitting pins of a serial interface of each slave device are respectively connected to a plurality of second data input pins of the MUX and receiving pins of a serial interface of each slave device are respectively connected to a plurality of second data output pins of the MUX, the master device communicates with one slave device via transmitting a corresponding selecting signal to the two selecting pins of the MUX to select one slave device.

1. Field of the Invention
The present invention relates to communication circuits, and particularly to a multi-channel communication circuit between a master device and a plurality of slave devices.
2. Description of Related Art
In communication circuits, serial interfaces such as RS232 serial interfaces are familiar communication interfaces for data communications between a master device such as a server and a plurality of slave devices such as uninterrupted power supplies (UPS).
However, this communication circuit only allows the master device to connect with one of the slave devices at any given time via the serial interfaces thereof. If the master device needs to access another slave device, the user must connect a serial interface of the master device to a serial interface of another slave device again, which is very inconvenient.
What is desired, therefore, is to provide a multi-channel communication circuit which can let a master device connect with a plurality of slave devices at the same time.


A method of managing lip synchronization error in a multimedia content delivery network includes identifying a video packet and an audio packet associated with the video packet and determining a synchronization offset between the audio and video packets at a first monitoring point in the network. The audio and video packets are then detected at a second monitoring point in the network and a second synchronization offset is determined. When a delta between the first synchronization offset and the second synchronization offset exceeds a threshold, lip synchronization error information may be automatically recorded and/or reported to a service provider and corrective action may be taken if potential sources of the lip synchronization error are within the domain of the service provider. The video packet may be identified by a timestamp within the packet and the audio packet may be identified by audio data within the audio packet.

When multimedia content is delivered over a distribution network to a plurality of end users, whether via satellite, cable, twisted copper, fiber, or another medium, audio components and video components may be segregated to improve network efficiencies. However, when segregated audio and video packets are transported across the network, random and systematic sources of error or delay may affect video and audio packets differently and can, therefore, negatively impact the synchronization. Because the most common or recognizable manifestation of the problem may be a detectable difference in timing between the visual perception of the movement of a speaker's lips and the audio perception of the corresponding sound, this problem is commonly referred to as lip synchronization error or, more simply, lip sync error.


A game control server apparatus includes an evolution information storing unit that stores a base character, a partner character and an evolved character associated with each other, the base character being converted to the evolved character by combining the base character and the partner character; and an evolution process management unit that coverts, upon accepting an evolution instruction of a base character possessed by a first player by combining the base character and a partner character possessed by another second player to evolve the base character from the first player, the base character to an evolved character that is associated with the base character and the partner character using the partner character of the second player under a condition that a process of paying reward from the first player to the second player is performed.

1. Field of the Invention
The present invention relates to a game control server apparatus.
2. Description of the Related Art
Conventionally, there is a game in which a character is combined with another character to be converted to a new character. Patent Document 1 discloses a technique in which a character that satisfies a predetermined condition is formed into a seed, and then a new character is generated by combining seeds.
Patent Document 2 discloses a technique in which an upper limitation value of level of a game card is increased (evolved) by combining game cards (game media) of the same kind.
However, conventionally, a user cannot convert a character or the like if the user does not have a character or the like to combine with. Thus, when a character or the like that is necessary for conversion is difficult to obtain, a burden for players is heavy. Further, conventionally, there is a room for improvement in activating communication between players.


An antenna device usable in a radio apparatus including a printed board includes a ground conductor of the printed board, a first partial element, a second partial element and a parasitic element. The first partial element is shaped into an area having a first side facing a side of the ground conductor and a second side directed to cross the side of the ground conductor, and is provided with a feed portion around a first end of the first side being closer to the second side. The second partial element branches off from the first partial element around one of two ends of the second side being farther from the feed portion, and is directed almost against a direction from the feed portion to a second end of the first side being farther from the second side. The parasitic element has an end grounded around the second end.

1. Field of the Invention
The present invention relates to an antenna device and a radio apparatus operable in multiple frequency bands, and in particular to a built-in type antenna device and a radio apparatus including the antenna device.
2. Description of the Related Art
There is a trend that mobile phones or personal computers (PCs) having radio capability have multiple purposes and multiple functions. The above trend requires an antenna device which may be operable in multiple frequency bands or in a broad frequency range.
In order to meet the above requirement, antenna devices designed to have multiple resonant frequencies (to be operable in multiple frequency bands) or to be operable in a broad frequency range are disclosed, e.g., in Japanese Patent Publication of Unexamined Applications (Kokai), No. 2004-172912 or No. 2004-201278.
More specifically, JP 2004-172912 discloses a multi-frequency (multi-band) antenna of an inverted F type formed by a feeding line, a short-circuiting line and a first open-ended line. The antenna of JP 2004-172912 further has a second open-ended line almost shaped into a rectangle and arranged on an opposite side of the feeding line as viewed from the first open-ended line. According to JP 2004-172912, it has been estimated by simulation that the antenna configured as described above may have resonances, e.g., at a 2.4 gigahertz (GHz) band and at a 5.2 GHz band.
JP 2004-201278 discloses a pattern antenna including an inverted F type antenna, an inverted L type antenna and a ground conductor which are conductive patterns formed on a surface of a printed board. The inverted F type antenna may be fed and excited. The inverted L type antenna is arranged to nearly surround the inverted F type antenna and may be excited as a parasitic element. According to JP 2004-201278, resonant frequencies of the inverted F type antenna and the inverted L type antenna may be determined by their element lengths so that the pattern antenna may have at least two resonant frequencies.
JP 2004-172912 discloses an embodiment of the multi-band antenna applied to a wireless local area network (WLAN). The arrangement of the second open-ended line being nearly rectangular and the first open-ended line on the one side and on the other side of the feeding line, respectively, may cause a parallel resonance. If the multi-band antenna is used in a lower frequency band such as a mobile phone antenna, the parallel resonance may disturb a broadband characteristic there.
As described above, the parasitic element of the pattern antenna of JP 2004-201278 is arranged to nearly surround the inverted F antenna of an element length being shorter than the length of the parasitic element. It may thus be understood, according to a paragraph "0035" of JP 2004-201278, that the inverted F antenna is arranged close to the parasitic element along a whole element length of the inverted F antenna.
If an element to be fed and a parasitic element are arranged in positions relative to each other as described above, though, it may be difficult to excite the parasitic element at a desired frequency due to effects of a voltage-coupling and a current-coupling which may cancel each other. If open ends of both of the elements are arranged separate in order to avoid such difficulty, it may be difficult to shape a radio apparatus including the elements as a built-in antenna into a low profile configuration.

Antenna device and radio apparatus operable in multiple frequency bands


A photosensitive member cartridge includes first and second side walls which rotatably support end portions of the photosensitive member in an axial direction of the photosensitive member, a rotating body disposed between the first side wall and the second side wall to face the photosensitive member, and a cartridge electrode which extends in the axial direction and disposed on the first side wall to be movable in the axial direction, and contacts the rotating body to supply electric power to the rotating body. The cartridge electrode includes a contact portion which contacts an end surface of the rotating body in the axial direction. The first side wall includes an abutting portion which abuts on the end surface of the rotating body. The cartridge electrode is configured such that the first contact portion is movable further than the abutting portion in the axial direction.

As an image forming apparatus employing an electro-photographic method, there has been known an image forming apparatus which includes a photosensitive member cartridge having a photosensitive member, and a developing cartridge for accommodating developer.
As an example of a photosensitive member cartridge to be mounted in that image forming apparatus, there has been known a process cartridge which includes a photosensitive drum, and a cleaning roller for electrically removing foreign materials such as residual toner or sheet powders attached on the circumferential surface of the photosensitive drum (see, for example, JP-A-2009-162911).
In this process cartridge, a cleaning roller electrode is provided for supplying a bias from a main body casing to the cleaning roller.


After a laser beam of a high-level laser beam is applied to a multilayer magneto-optical recording medium to record information thereon, a laser beam of a laser power lower than the laser power of a reading laser beam is applied or substantially no laser beam is applied for a period of time .tau..sub.0. If one channel clock period or the period in which the high-level laser beam is of the second laser power is applied is .tau..sub.w, then the ratio R=(.tau..sub.0 /.tau..sub.w).times.100 is selected to be in the range from 15 to 70%.

1. Field of the Invention
The present invention relates to a method of magneto-optically recording information on a magneto-optical recording medium with an intensity-modulated laser beam.
2. Description of the Prior Art
There have been proposed magneto-optical recording methods capable of overwriting information on multilayer magneto-optical recording mediums with an intensity-modulated laser beam so that newly recorded information replaces the previously recorded information (see, for example, Japanese laid-open patent publications Nos. 62-175948 and 63-52355).
As shown in FIG. 1 of the accompanying drawings, a multilayer magneto-optical recording medium 1, such as a magneto-optical disk, for magneto-optically recording information thereon comprises a transparent substrate 2 such as a glass substrate, a resin substrate, or the like, a dielectric film 3 disposed on one surface of the transparent substrate 2, a recording and reproducing layer 4 and a recording assistance layer 5 with perpendicular magnetic anisotropy which are successively deposited on the dielectric film 3 by way of continuous sputtering or the like, and a protective film 6 such as a nonmagnetic metallic film, a dielectric film, or the like coated on the surface of the recording assistance layer 5.
The recording and reproducing layer 4 may be made of a rare-earth-rich (RE-rich) material such as TbFeCo, for example, which has a large coercive force H.sub.C1 at normal temperature T.sub.R (ranging from -20.degree. to 60.degree. C.) and a low Curie temperature T.sub.C1. The recording assistance layer 5 may be made of a transition-metal-rich (TM-rich) material such as GdTbFeCo, for example, which has a small coercive force H.sub.C2 at normal temperature T.sub.R and a high Curie temperature T.sub.C2.
Information is recorded on the magneto-optical recording medium 1 as follows: As shown in FIG. 2 of the accompanying drawings, the recording assistance layer 5 is magnetized in an upward direction as indicated by the arrows, and the recording and reproducing layer 4 is magnetized in upward and downward directions as indicated by the arrows. The layers 4, 5 which are magnetized in the upward direction are combined in a first state ST.sub.A, and the layers 4, 5 which are magnetized in the downward and upward directions, respectively, are combined in a second state ST.sub.B. The first and second states ST.sub.A, ST.sub.B serve to represent the recorded information "0" and the recorded information "1", respectively.
A process of recording the information "0" on the magneto-optical recording medium 1 which is in either the first state ST.sub.A or the second state ST.sub.B will be described below. First, a laser beam having a first laser power P.sub.L which is sufficient to achieve a temperature T.sub.ER that is higher than the Curie temperature T.sub.C1 of the recording and reproducing layer 4 and lower than the Curie temperature T.sub.C2 of the recording assistance layer 5, is applied to the magneto-optical recording medium 1 for a predetermined period of time to bring the recording and reproducing layer 4 into a third state ST.sub.C in which the direction of magnetization is unstable.
Thereafter, the magneto-optical recording medium 1 is cooled on its own accord thereby to enable the exchange force acting in the boundary between the layers 4, 5 to orient the direction of magnetization of the recording and reproducing layer 4 in the same upward direction as the recording assistance layer 5. In this manner, the magneto-optical recording medium 1 is brought from the first state ST.sub.A representing "0" or the second state ST.sub.B representing 1"` to the first state ST.sub.A representing "0".
To record the information "1" on the magneto-optical recording medium 1 which is in either the first state ST.sub.A or the second state ST.sub.B, the magneto-optical recording medium 1 is irradiated for a predetermined period of time with a laser beam having a second laser power P.sub.H, higher than the first laser power P.sub.L, which is sufficient to achieve a temperature T.sub.REC that is close to the Curie temperature T.sub.C2 of the recording assistance layer 5. At the same time, a downward recording magnetic field H.sub.REC ranging from 300 to 500 Oe, for example, higher than the coercive force H.sub.CR of the recording assistance layer 5 at the temperature T.sub.REC is applied to the magneto-optical recording medium 1.
Now, the magneto-optical recording medium 1 is brought into a fourth state ST.sub.D in which the direction of magnetization of the recording and reproducing layer 4 is unstable and the recording assistance layer 5 is magnetized downwardly. Thereafter, the magneto-optical recording medium 1 is cooled on its own accord, enabling the exchange force acting in the boundary between the layers 4, 5 to orient the direction of magnetization of the recording and reproducing layer 4 in the same downward direction as the recording assistance layer 5. Such a magnetized condition of the layers 4, 5 is referred to as a fifth state ST.sub.E.
Thereafter, an upward initializing magnetic field H.sub.ini ranging from 3 to 5 kOe which is smaller than the coercive force H.sub.C1 of the recording and reproducing layer 4 at the normal temperature T.sub.R and larger than the coercive force H.sub.C2 of the recording assistance layer 5 at the normal temperature T.sub.R is applied to the magneto-optical recording medium 1 to orient the direction of magnetization of only the recording assistance layer 5 upwardly. In this manner, the magneto-optical recording medium 1 is brought from the first state ST.sub.A representing "0" or the second state ST.sub.B representing "1" to the second state ST.sub.B representing "1".
According to the above magneto-optical recording process, the direction of magnetization of the layers 4, 5 can be controlled into an upward or downward direction by controlling the intensity of the laser power. Therefore, using a single laser beam, new information can be overwritten directly on the magneto-optical recording medium 1 to replace the old recorded information, without any separate process of erasing the old recorded information.
In the above magneto-optical recording process, the magneto-optical recording medium 1 is always irradiated with either the laser beam of the first low-level laser power P.sub.L to record "0" or the laser beam of the second high-level laser power P.sub.H to record "1" while erasing the previously recorded information. Therefore, the temperature distribution of the magneto-optical recording medium 1 which is irradiated with pulses of the laser beam tends to be in a broader range than it is according to a general magneto-optical recording process in which only the laser beam of the second laser power P.sub.H is switched on and off.
More specifically, it is assumed that after the laser beam of the second laser power P.sub.H is applied to the magneto-optical recording medium 1 to record the information "1", the laser beam of the first laser power P.sub.L is applied to record erase the recorded information, i.e., to record the information "0". The laser beam of the first laser power P.sub.L is applied before a region around the pit in the magneto-optical recording medium 1 whose temperature has been increased by the laser beam of the second laser power P.sub.H is sufficiently cooled down. At this time, due to the thermal interference between the laser beams, the recording and reproducing layer 4 tends to be heated to a temperature that exceeds the Curie temperature T.sub.C1 at which the direction of magnetization of the recording and reproducing layer 4 is unstable, and that is close to the Curie temperature T.sub.C2 of the recording assistance layer 5.
When information is overwritten according to the conventional magneto-optical recording process, pits formed in the recording and reproducing layer 4 is liable to be irregular in configuration, resulting in a poor C/N ratio, i.e., higher noise. If two adjacent pits are closely spaced from each other, it is difficult to recognize the pits separately, and hence the error rate is increased.
The region of the magneto-optical recording medium 1 which is irradiated with the laser beam of the first laser power P.sub.L is thermally affected to a different degree depending on the interval at which the laser beam of the second laser power P.sub.H is applied. Since the region of the magneto-optical recording medium 1 is thermally affected to a different degree, an optimum range of the first laser power P.sub.L varies with the result that the range (margin) of the first laser power P.sub.L which is optimum for various laser pulse intervals becomes narrow.
While it is necessary to set the low-level laser power P.sub.L accurately to a constant level, it is actually difficult to select such a constant level and set the laser power to the selected constant level. The narrow margin for the low-level laser power is responsible for an increase in the BER (Byte Error Rate).
In an attempt to eliminate the above drawbacks, there has been proposed a magneto-optical recording process as disclosed in Japanese laid-open patent publication No. 2-244443. According to the disclosed magneto-optical recording process, desired information is magneto-optically recorded on a magneto-optical recording medium with an intensity-modulated laser beam, and the laser beam is turned off for a predetermined period of time .tau..sub.0 following the application of the laser beam of the high-level laser power P.sub.H.


The present invention relates to a configuration utilizing a driven element that is driven by a current. Specifically, there is provided a pixel circuit having a driven element and a current-drive transistor for supplying a current for driving the driven element to a current injection terminal of the driven element, a voltage buffer, a current signal line for supplying a current signal to the pixel circuit, and a wiring for connecting an output of the voltage buffer and a gate electrode of the current drive transistor. The pixel circuit has a switch for controlling connection between the voltage buffer and the gate electrode of the current-drive transistor, and an input terminal of the voltage buffer is connected to the current signal line.

1. Field of the Invention
The present invention relates to a circuit for driving a driven element that is driven by injecting a current to the same. The invention also relates to a display apparatus utilizing the circuit.
2. Description of the Related Art
One type of driven elements which can be driven by injecting a current are electroluminescent elements (hereinafter referred to as EL elements) which are made to emit light by injecting a current. A circuit for driving such an element may be constituted by an insulated gate field effect transistor such as a TFT (thin film transistor).
EL elements are used in panel type image display systems (hereinafter referred to as EL panels) in which pixel circuits constituted by TFTs are two-dimensionally arranged.
A configuration utilizing EL elements is disclosed in U.S. Pat. No. 6,373,454.

Drive circuit, display apparatus, and information display apparatus


An engine control module is associated with a particular engine system, and used to store information concerning manufacturing instructions for manufacturing the engine system and as-built information about the particular engine system. The engine control module also stores engine system operating instructions operable to enable the engine control module to control one or more aspects of the engine system operation.

Because of the large number of components in an engine system and the relative complexity of each step in the manufacturing process, there is a need to methodically manage and communicate information relating to the engine system's manufacture throughout the manufacturing process. Managing and communicating this information between the numerous steps in manufacturing is complex. The complexity is compounded in a manufacturing process that manufactures different configurations of engine systems using the same manufacturing stations, because information concerning each engine system configuration must be communicated between the stations and coordinated with the engine system configurations. The complexity is further compounded when engine systems of a particular general configuration are customized to be unique from others of the same general configuration. For example, a manufacturing facility may manufacture three different models of engine systems that differ in general configuration, and within each of the three different models, particular ones may be customized to specific customer specifications. Ensuring that a particular engine system is built according to its specified configuration and further customized as requested by the customer requires detailed documentation and a system by which the information is communicated throughout the manufacturing process to the proper workers.
Furthermore, there is a desire to have documentation describing the engine system as-built. Such as-built information adds to the volume of information and the difficulty of maintaining a system by which the information is communicated throughout the manufacturing process.
Therefore, there is need to manage information relating to an engine system's manufacture and its communication throughout the manufacturing process.

Engine control module and method for use in engine system manufacture


A rack system is disclosed for mounting various devices. The rack system comprises at least one front vertical support column and at least one rear vertical support column. A rail is deployed between the front vertical support column and the rear vertical support column. Additionally, a latching system is provided that enables secure engagement of the rail and easy removal of the rail.

Various racks are used to hold multiple devices in an organized manner. For example, racks are utilized in mounting servers and/or other computer based devices. The servers or other devices are mounted on horizontal rails connected to vertical support columns. The rails are attached to the vertical support columns by, for example, fasteners, such as screws, bolts and/or nuts. With this type of rail, tools are required to attach the screws, bolts and nuts.
In other rail designs, multiple loose parts are assembled to complete the rail assembly before installing it on the rack. Also, the installation technician often must walk back and forth between the front and the rear of the rack to install each end of the rail assembly to the vertical support columns. In some applications, two installation technicians may be required to complete the task.

Hewlett-Packard Development Company, L.P.