The present invention provides a fluorine-containing surface treatment composition comprising a surface treatment component and a solvent component wherein the solvent component contains 5 wt. % or more of a chlorine-free, non-flammable halogen-containing solvent which has an ozone depletion potential (ODP) of 0.03 or less, a 100-year integrated global warming potential (GWP) value of 500 or less, and a KB value of 5 or more. The fluorine-containing surface treatment composition of the present invention is a surface treatment agent that is extremely unlikely to cause ozone layer depletion and global warming, has excellent storage stability and excellent performance characteristics as a surface treatment agent and is highly safe due to the non-flammability or flame retardancy thereof.

The present invention relates to a fluorine-containing surface treatment composition, a product to be used for surface treatment comprising the surface treatment composition, and a process for surface treatment.
Fluorine-containing surface treatment compositions are applied to various substrate surfaces to impart thereto various properties characteristic of fluorine-containing compounds, such as low surface energy, non-adhesion (mold releasability), water repellency and oil repellency. For example, with use of metal or other items as substrates, the fluorine-containing surface treatment compositions find applications as mold release agents, resin adhesion inhibitors, flux barrier agents, anti-adhesion agents, antiblocking agents, rear surface treatment agents, antitacking agents, electric wire stripping agents and lubricants.
Chlorofluorocarbons have been widely used as solvents for solvent-based fluorine-containing surface treatment compositions because the chlorofluorocarbons are less toxic, nonflammable and chemically stable. Particularly CFC-113, which has a moderate boiling point, has been widely used. However, ozone layer depletion by specific chlorofluorocarbons such as CFC-113 became a problem and production of such chlorofluorocarbons has been discontinued on a world-wide scale.
Under such circumstances, much study was carried out on solvents which may replace the chlorofluorocarbons. Since it was considered that hydrochlorofluorocarbons could be a replacement, various fluorine-containing surface treatment compositions containing HCFC-141b as a solvent were developed. Although hydrochlorofluorocarbons have low ozone depletion potential (ODP), it does not mean that the hydrochlorofluorocarbons do not cause any ozone depletion. For this reason, reduction or total abolition of hydrochlorofluorocarbons has been decided.
In such circumstances, further research was carried out and fluorine-containing surface treatment compositions containing solvents such as perfluorocarbon (PFC) and perfluoroether (PFE) were developed (e.g., xe2x80x9cDAIFREE GF-6400xe2x80x9d manufactured by Daikin Industries, Ltd., Japanese Unexamined Patent Publication No. 109158/1997, etc.). However, perfluoro-solvents were found to cause an environmental problem of greatly affecting global warming, although the perfluoro-solvents do not cause ozone layer depletion. For this reason, limitation on perfluoro compound emissions has been decided, and it is currently difficult to use such perfluoro-solvents.
A primary object of the present invention is to provide a fluorine-containing surface treatment composition that has excellent storage stability and excellent performance characteristics as a surface treatment agent and is highly safe due to the non-flammability or flame retardancy thereof, the composition causing hardly any ozone layer depletion and global warming.
The inventors of the present invention carried out intensive research in view of the above problems and finally found the following. The object can be achieved with a fluorine-containing surface treatment composition comprising a fluorine-containing surface treatment component and a solvent component, wherein the solvent component contains 5 wt. % or more of a chlorine-free, non-flammable halogen-containing solvent which has an ozone depletion potential (ODP) of 0.03 or less, a 100-year integrated global warming potential (GWP) value of 500 or less, and a KB value of 5 or more. The present invention has been accomplished based on this finding.
The present invention provides the following fluorine-containing surface treatment composition, product to be used for surface treatment comprising the surface treatment composition, and process for surface treatment.
1. A fluorine-containing surface treatment composition comprising a surface treatment component and a solvent component, wherein the solvent component contains 5 wt. % or more of a chlorine-free, non-flammable halogen-containing solvent which has an ozone depletion potential (ODP) of 0.03 or less, a 100-year integrated global warming potential (GWP) value of 500 or less, and a KB value of 5 or more, the composition being used for purposes other than a water-repellent and an oil-repellent.
2. The fluorine-containing surface treatment composition according to item 1 wherein the halogen-containing solvent has a boiling point of 0xc2x0 C. to 150xc2x0 C.
3. The fluorine-containing surface treatment composition according to item 1 or 2 wherein the surface treatment component comprises at least one species selected from:
(1) phosphorus-containing compounds having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups;
(2) highly fluorinated organic compounds; and
(3) polymers prepared using as a monomer component a compound having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups.
4. The fluorine-containing surface treatment composition according to item 1 or 2 wherein
the surface treatment component contains 5 wt. % or more of at least one component selected from
(1) phosphorus-containing compounds having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups and
(2) highly fluorinated organic compounds, and
the solvent component contains 50 wt. % or more of hydrofluoroether.
5. The fluorine-containing surface treatment composition according to item 4 wherein the surface treatment component comprises:
at least one component selected from
(1) phosphorus-containing compounds having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups and
(2) highly fluorinated organic compounds; and
at least one component selected from (i) silicone compounds and (ii) waxes.
6. The fluorine-containing surface treatment composition according to item 5 wherein the solvent component comprises hydrofluoroether and at least one solvent selected from aromatic solvents, petroleum solvents, ketone solvents and bromine-containing solvents.
7. The fluorine-containing surface treatment composition according to item 6 wherein
the surface treatment component contains 30-95 wt. % of at least one component selected from (1) phosphorus-containing compounds having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups and (2) highly fluorinated organic compounds and 70-5 wt. % of at least one component selected from (i) silicone compounds and (ii) waxes; and
the solvent component contains 50-90 wt. % of hydrofluoroether and 10-50 wt. % of at least one solvent selected from aromatic solvents, petroleum solvents, ketone solvents and bromine-containing solvents.
8. The fluorine-containing surface treatment composition according to item 1 or 2 wherein
the surface treatment component contains 5 wt. % or more of (3) a polymer prepared using as a monomer component a compound having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups; and
the solvent component contains 50 wt. % or more of a bromine-containing solvent.
9. The surface treatment composition according to item 8 wherein the surface treatment component comprises:
(3) a polymer prepared using as a monomer component a compound having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups; and
at least one component selected from (2) highly fluorinated organic compounds, (i) silicone compounds and (ii) waxes.
10. The surface treatment composition according to item 9 wherein the surface treatment component contains:
30-95 wt. % of (3) a polymer prepared using as a monomer component a compound having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups; and
70-5 wt. % of at least one component selected from (2) highly fluorinated organic compounds, (i) silicone compounds and (ii) waxes.
11. The surface treatment composition according to item 8 wherein the bromine-containing solvent is a C1-3 halogenated hydrocarbon having at least one bromine atom.
12. The surface treatment composition according to item 8 wherein the bromine-containing solvent is bromopropane.
13. The surface treatment composition according to item 8 wherein (3) the polymer prepared using as a monomer component a compound having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups is a copolymer of at least one fluorine-containing monomer selected from polyfluoroalkyl-containing (meth)acrylic esters, polyfluoroalkenyl-containing (meth)acrylic esters, polyfluoroalkyl-containing vinyl compounds and polyfluoroalkenyl-containing vinyl compounds, and another monomer copolymerizable therewith, the proportion of the fluorine-containing monomer being 20-95 parts by weight, based on 100 parts by weight of the total monomer component.
14. The surface treatment composition according to item 8 wherein (3) the polymer prepared using as a monomer component a compound having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups is a polymer of at least one fluorine-containing monomer selected from polyfluoroalkyl-containing epoxy monomers and polyfluoroalkenyl-containing epoxy monomers, or a copolymer of the fluorine-containing monomer and another monomer copolymerizable therewith, the proportion of the fluorine-containing monomer being 20-100 parts by weight, based on 100 parts by weight of the total monomer component.
15. The fluorine-containing surface treatment composition according to item 5 which is used as a mold release agent, an electric wire stripping agent or a lubricant.
16. The fluorine-containing surface treatment composition according to item 9 which is used as a mold release agent, an electric wire stripping agent or a lubricant.
17. A solvent for a fluorine-containing surface treatment composition used for purposes other than a water-repellent and an oil-repellent, which comprises a chlorine-free, non-flammable halogen-containing solvent having an ozone depletion potential (ODP) of 0.03 or less, a 100-year integrated global warming potential (GWP) value of 500 or less, and a KB value of 5 or more.
18. A product to be used for surface treatment comprising a container having a mechanism for ejecting a liquid from the container, the container containing the surface treatment composition according to item 1.
19. The product according to item 18 wherein the container is an aerosol container.
20. A surface treated article obtained by surface-treating an article with the surface treatment composition according to item 1.
21. A process for surface treatment of an article to be treated, which comprises treating the article with the surface treatment composition according to item 1, followed by drying.
According to the fluorine-containing surface treatment composition of the present invention, it is essential to use as a solvent component a chlorine-free, non-flammable halogen-containing solvent which has an ozone depletion potential (ODP) of 0.03 or less, a 100-year integrated global warming potential (GWP) value of 500 or less, and a KB value of 5 or more. Use of such a solvent provides a fluorine-containing surface treatment composition with high safety and good storage stability, the composition being extremely unlikely to cause ozone layer depletion and global warming.
In the above definition, the global warming potential (GWP) value is a cumulative total over a period of 100 years, based on the GWP of carbon dioxide gas calculated as 1. The KB value is used for showing dissolving capability of diluents in lacquer and paint industries. The KB value indicates how many cubic centimeters of a diluent is necessary to cause kauri gum to precipitate at 25xc2x0 C. using 20 g of a standard solution containing kauri gum in butanol (American Gum Importor""s Inc.). The higher the value is, the higher the dissolving capability is.
It is preferable that the halogen-containing solvent have a boiling point of about 0xc2x0 C. to about 150xc2x0 C., more preferably about 20xc2x0 C. to about 100xc2x0 C., further more preferably about 40xc2x0 C. to about 80xc2x0 C. A solvent with a boiling point in the above-mentioned range is easy to handle and provides a moderate drying speed of the surface treated article, thus being advantageous in ease of use.
Examples of chlorine-free, non-flammable halogen-containing solvents having an ozone depletion potential (ODP) of 0.03 or less, a global warming potential (100-year integrated GWP value) of 500 or less, and a KB value of 5 or more and having a boiling point of 0xc2x0 C. to 150xc2x0 C. include 1-bromopropane (boiling point: 71xc2x0 C.), 2-bromopropane (boiling point: 59xc2x0 C.-60xc2x0 C.), 1,2-dibromopropane (boiling point: 140xc2x0 C.-142xc2x0 C.), 1-bromo-2-fluoroethane (boiling point: 71xc2x0 C.-72xc2x0 C.), 1-bromo-3-fluoropropane (boiling point: 99xc2x0 C.-101xc2x0 C.), 1,2-dibromofluoroethane (boiling point: 122.5xc2x0 C.), 1,2-dibromo-1,1-difluoroethane (boiling point: 92xc2x0 C.-93xc2x0 C.), dibromomethane (boiling point: 97xc2x0 C.) and like bromine-containing solvents; nanofluorobutyl-methyl ether (boiling point: 60xc2x0 C., product name: HFE-7100 (manufactured by 3M)), nanofluorobutyl-ethyl ether (boiling point: 78xc2x0 C., product name: HFE-7200 (manufactured by 3M)), pentafluoroethyl-methyl ether (boiling point: 5.6t), heptafluoropropyl-methyl ether (boiling point: 34.2xc2x0 C.), heptafluoroisopropyl-methyl ether (boiling point: 29.4xc2x0 C.) and like hydrofluoroethers. Particularly preferred in view of commercial availability, safety and other physical properties are 1-bromopropane (boiling point: 71xc2x0 C.; ozone depletion potential (ODP): 0.021; global warming potential (100-year integrated GWP value): about 0.3; KB value: 125; nonflammable); nanofluorobutyl-methyl ether (boiling point: 60xc2x0 C.; ozone depletion potential (ODP): 0; global warming potential (100-year integrated GWP value): 500; KB value: 10; nonflammable; product name: HFE-7100 (manufactured by 3M)); nanofluorobutyl-ethyl ether (boiling point: 78xc2x0 C.; ozone depletion potential (ODP): 0; global warming potential (100-year integrated GWP value): 100; KB value: 10; nonflammable; product name: HFE-7200 (manufactured by 3M)); and the like.
The halogen-containing solvents may be used singly or in combination of two or more.
The solvent component may include, in addition to the above-mentioned halogen-containing solvents, other solvents as cosolvents. Examples of useful cosolvents include petroleum solvents such as n-hexane, n-heptane, n-decane, isooctane, petroleum ether and gasoline for industrial use; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone and methylethylketone; alcohol solvents such as ethanol and isopropanol; aromatic solvents such as toluene and xylene; glycol (ether) solvents such as ethylene glycol, propylene glycol and propylene glycol monomethyl ether. The solvents may be used singly or in combination of two or more.
According to the composition of the invention, the proportion of the halogen-containing solvent in the solvent component is 5 wt. % or more, preferably 10 wt. % or more, further more preferably 20 wt. % or more, based on 100 wt. % of the total solvent component. The upper limit of the halogen-containing solvent can be 100 wt. %. Use of less than 5 wt. % of the halogen-containing solvent is unsuitable because it tends to be difficult to retain good storage stability while maintaining essential properties required of a fluorine-containing surface treatment composition, such as low surface energy, non-adhesion (mold releasability), water repellency and oil repellency, thus failing to achieve the object of the present invention.
The surface treatment component used as an active ingredient in the fluorine-containing surface treatment composition of the invention may be selected from components of various known fluorine-containing surface treatment agents, which may be used singly or in combination in accordance with the intended use.
According to the present invention, it is particularly preferable to use a surface treatment component comprising at least one component selected from:
(1) phosphorus-containing compounds having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups;
(2) highly fluorinated organic compounds; and
(3) polymers prepared using as a monomer component a compound having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups.
The surface treatment component of the invention may comprise, in addition to at least one surface treatment component selected from the components (1) to (3), other surface treatment components such as (i) silicone compounds and (ii) waxes, in accordance with the intended use. When the surface treatment component contains other components in addition to at least one of the components (1) to (3), the proportion of at least one of the components (1) to (3) is preferably 5 wt. % or more, more preferably 20 wt. % or more, based on 100 wt. % of the total surface treatment component. When the surface treatment component comprises 5 wt. % or more of at least one of the components (1) to (3), the composition has improved stability of performance characteristics such as low surface energy, non-adhesion (mold releasability), water repellency and oil repellency.
The total surface treatment component is preferably about 0.3 to about 30 wt. %, based on 100 wt. % of the total surface treatment composition of the present invention.
According to the present invention, when the surface treatment component comprises at least one component selected from (1) phosphorus-containing compounds having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups and (2) highly fluorinated organic compounds, it is particularly preferable to use a solvent component containing a hydrofluoroether, among the aforementioned halogen-containing solvents. Use of such a solvent component improves the solubility of the surface treatment component whereby uniform coating film is formed with ease, thus achieving improved performance characteristics such as low surface energy, non-adhesion (mold releasability), water repellency and oil repellency and also whereby good storage stability is provided. In this case, the hydrofluoroether is preferably used in a proportion of 50 wt. % or more, more preferably 70 wt. % or more, based on the total solvent.
When the composition comprises, as a surface treatment component, at least one component selected from (1) phosphorus-containing compounds having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups and (2) highly fluorinated organic compounds, and the composition is used as a mold release agent, an electric wire stripping agent, a lubricant or the like, it is preferable that the composition further comprise at least one surface treatment component selected from (i) silicone compounds and (ii) waxes. In this case, the surface treatment component preferably contains about 30-95 wt. % of at least one component selected from (1) phosphorus-containing compounds having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups and (2) highly fluorinated organic compounds, and about 70-5 wt. % of at least one component selected from (i) silicone compounds and (ii) waxes, based on the total surface treatment component. When the composition contains the components in such proportions, the composition has excellent performance characteristics such as low surface energy, non-adhesion (mold releasability), water repellency and oil repellency and also has excellent properties such as separability in the coating film, peelability and slipperiness, thus being suitable for use as mold release agents, electric wire stripping agents, lubricants and the like.
When the composition comprising at least one component selected from (i) silicone compounds and (ii) waxes contains hydrofluoroether as the only solvent component, the silicone compounds, waxes or other components may not be sufficiently dissolved. In this case, by using, in addition to the hydrofluoroether, at least one cosolvent selected from the aforementioned aromatic solvents (e.g., toluene, xylene), petroleum solvents, ketone solvents and bromine-containing solvents, improvement in solubility, stability of performance characteristics and storage stability can be achieved. The cosolvent is preferably used in a proportion of about 10-50 wt. %, based on the total solvent.
When the surface treatment component comprises (3) a polymer prepared using as a monomer component a compound having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups, it is preferable to use a solvent component containing a bromine-containing solvent, among the aforementioned halogen-containing solvents. Use of such a solvent component improves the solubility of the surface treatment component, whereby uniform coating film is formed with ease, thus achieving stability of performance characteristics such as low surface energy, non-adhesion (mold releasability), water repellency and oil repellency and also whereby good storage stability is provided. In this case, the bromine-containing solvent is preferably used in a proportion of 50 wt. % or more, more preferably 70 wt. % or more, based on the total solvent.
Preferred examples of bromine-containing solvents are C1-3 halogenated hydrocarbons having at least one bromine atom. Especially preferred are bromopropanes such as 1-bromopropane, 2-bromopropane and 1,2-dibromopropane. Use of such a solvent particularly provides improved stability of performance characteristics such as low surface energy, non-adhesion (mold releasability), water repellency and oil repellency due to the formation of uniform coating film and also provides especially good storage stability.
When the composition contains, as a surface treatment component, (3) a polymer prepared using as a monomer component a compound having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups, and the composition is used as a mold release agent, an electric wire stripping agent, a lubricant or the like, it is preferable to further contain at least one surface treatment component selected from (2) highly fluorinated organic compounds, (i) silicone compounds and (ii) waxes. In this case, the surface treatment component preferably contains about 30-95 wt. % of (3) a polymer prepared using as a monomer component a compound having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups; and about 70-5 wt. % of at least one component selected from (2) highly fluorinated organic compounds, (i) silicone compounds and (ii) waxes, based on the total surface treatment component. When the composition contains the components in such proportions, the composition has excellent performance characteristics such as low surface energy, non-adhesion (mold releasability), water repellency and oil repellency and also has excellent properties such as separability in the coating film, peelability and slipperiness, thus being suitable for use as mold release agents, electric wire stripping agents and lubricants.
The surface treatment component in the composition of the present invention will be described below in more detail.
(1) Phosphorus-containing Compound Having at Least One Fluorine-containing Group Selected from Polyfluoroalkyl Groups and Polyfluoroalkenyl Groups
The terms xe2x80x9cpolyfluoroalkylxe2x80x9d and xe2x80x9cpolyfluoroalkenylxe2x80x9d are used herein to refer to alkyl groups containing at least two fluorine atoms, and alkenyl groups containing at least two fluorine atoms, respectively. Preferably, each of the alkyl group and alkenyl group is a straight or branched chain group having 3 to 21 carbon atoms.
Examples of phosphorus-containing compounds include phosphoric esters, phosphonic acid derivatives, phosphinic acid derivatives and salts thereof. The compounds may be used singly or in combination of two or more.
The above-mentioned compounds will be described below.
(a) Examples of phosphoric esters or salts thereof include compounds represented by the following formula:
wherein Rf is a C3-21 straight or branched chain polyfluoroalkyl or polyfluoroalkenyl group, M is an alkali metal atom (e.g., sodium or potassium), an ammonium group or a substituted ammonium (substituted by, for example, a C1-5 alkyl group or a C1-5 alkoxy group),
R1 is a C1-5 alkyl group,
R2 is a C1-10 alkylene group or xe2x80x94CH2CH(OR3)CH2xe2x80x94 wherein R3 is a hydrogen atom or a C1-10 alkyl group,
j is 1, 2 or 3,
l is 2, 1 or 0 and is less than or equal to (3xe2x88x92j),
k is 2, 1 or 0 and is less than or equal to 3xe2x88x92(j+l),
t is 3xe2x88x92(J+l+k), and
R4 is a C1-10 alkylene group.
Specific examples of the compounds of formulas (1) to (2) are shown below.
(b) Examples of phosphonic acid derivatives and salts thereof include compounds represented by the following formulas:
RfR2PO(OR1)m(OH)n(OM)u
RfO⊚CH2PO(OR1)m(OH)n(OM)u
wherein Rf, R2, R1 and M are as defined above,
m is 2, 1 or 0,
n is 2, 1 or 0 and is less than or equal to (2xe2x88x92m), and
u is 2xe2x88x92(m+n).
Specific examples of the compounds of formulas (3) to (4) are shown below.
(c) Examples of phosphinic acid derivatives and salts thereof include compounds represented by the following formulas:
wherein Rf, R2, R1 and M are as defined above,
p is 1 or 0,
q is 2xe2x88x92p,
s is 1 or 0
r is 1 or 0 and is less than or equal to (1xe2x88x92r), and
v is 1xe2x88x92(s+r).
Specific examples of the compounds of formulas (5) to (6) are shown below.
(2) Highly Fluorinated Organic Compound:
The highly fluorinated organic compound includes, for example, fluorine-containing oils, fluoroolefin telomers, and fluoroalkanes. Examples of fluorine-containing oils include fluoropolyethers, fluorochloro polyethers and like fluorine-containing polyether oils, fluorochloroolefin telomers, fluoroalkanes and the like. The compounds may be used singly or in combination of two or more.
The highly fluorinated organic compound may be liquid or solid. The highly fluorinated organic compound preferably has a boiling point of 180xc2x0 C. or higher, more preferably 200xc2x0 C. or higher.
Highly fluorinated organic compounds are known. Commercially available are Demnum (manufactured by Daikin Industries, Ltd.), Krytox (manufactured by Du Pont), Fomblin (manufactured by Mont Edison), Akulan (manufactured by Allied Corporation) and the like.
The highly fluorinated organic compounds will be described below in more detail.
I. Fluoropolyethers and fluorochloro polyethers include, for example, the following compounds (a) to (f).
(a) A polymer of 2,2,3,3-tetrafluorooxetane whose main portion (portion except for terminal groups) is composed of 2-200 repeating units represented by xe2x80x94CH2CF2CF2Oxe2x80x94 (this polymer is described in Japanese Unexamined Patent Publication No. 137928/1985; hereinafter referred to as polymer (1)).
Specific examples thereof include:
a polymer comprising repeating units represented by xe2x80x94CH2CF2CF2Oxe2x80x94 and having a number average molecular weight of 1.5xc3x97104;
a mixture of C3F7OCF(CF3)CF2O(CH2CF2CF2O)pCH2CF2COF (wherein p is an integer of 1 to 10);
a mixture of F(CH2CF2CF2O)qCH2CF2COOCH3 (wherein q is an integer of 0 to 9);
a polymer comprising repeating units represented by xe2x80x94CH2CF2CF2Oxe2x80x94 and having a number average molecular weight of 1.0xc3x97104;
a mixture of I(CH2CF2CF2O)rCH2CF2COOCH3 (wherein r is an integer of 0 to 5);
a mixture of CF3CF2CF2O(CH2CF2CF2O)nCH2CF2COOCH3 (wherein n is an integer of 1 to 8);
a mixture of F(CH2CF2CF2O)m(CF(CF3)CF2O)nCF(CF3)COOCH3 (wherein m is an integer of 2 to 9 and n is an integer of 0 to 3);
a mixture of (CF3)2CFO(CH2CF2O)nCH2CF2COOCH3 (wherein n is an integer of 1 to 8); and
a mixture of C3F7OCFCF2O(CH2CF2CF2O)pCH2CF3 (wherein p is an integer of 1 to 10).
(b) A polymer obtained by substituting part or all of the hydrogen atoms in the polymer (1) with fluorine atoms, wherein the main portion of the polymer (portion except for terminal groups) comprises repeating units represented by xe2x80x94CF2CF2CF2Oxe2x80x94 or xe2x80x94CHFCF2CF2Oxe2x80x94 and is composed of at least one repeating unit selected from xe2x80x94CF2CF2CF2Oxe2x80x94, xe2x80x94CHFCF2CF2Oxe2x80x94 and xe2x80x94CH2CF2CF2Oxe2x80x94, the total of the repeating units (degree of polymerization) being 2 to 200 (this polymer is described in Japanese Unexamined Patent Publication No. 202122/1985).
Specific examples thereof include:
(CH2CF2CF2O)pxe2x80x94(CHFCF2CF2O)q (p+q is 25 on an average, p:q=7:3, x number of units and y number of units may be arranged in a random order);
(CF2CF2CF2O)qxe2x80x94(CHFCF2CF2O)r (q+r is 25 on an average, p:r=5:1, x number of units and y number of units may be arranged in a random order);
F(CF2CF2CF2O)nCF2CF3 (n is 23 on an average);
C3F7OCF(CF3)CF2O(CH2CF2CF2O)nxe2x80x94(CHFCF2CF2O)mCHFCF3 (m+n is 7 on an average, m:n=1:4);
C3F7OCF(CF3)CF2O(CH2CF2CF2O)nCF2CF3 (n is 7 on an average);
F(CF2CF2CF2O)2CF2CF3;
F(CF2CF2CF2O)nCF2CF3 (n is 2.2 on an average);
F(CF2CF2CF2O)nCF2CF3 (n is 25 on an average);
(c) A polymer obtained by substituting part or all of the hydrogen atoms in the polymer (1) with chlorine atoms, wherein the main portion of the polymer (portion except for terminal groups) comprises repeating units represented by xe2x80x94CCl2CF2CF2Oxe2x80x94 or xe2x80x94CHClCF2CF2Oxe2x80x94 and is composed of at least one repeating unit selected from xe2x80x94CCl2CF2CF2Oxe2x80x94, xe2x80x94CHClCF2CF2Oxe2x80x94 and xe2x80x94CH2CF2CF2Oxe2x80x94, the total of the repeating units (degree of polymerization) being 2 to 200 (this polymer is described in Japanese Unexamined Patent Publication No. 113616/1986).
A polymer obtained by substituting part or all of the hydrogen atoms in the polymer (1) with fluorine atoms and chlorine atoms, wherein the main portion of the polymer (portion except for terminal groups) comprises repeating units represented by xe2x80x94CF2CF2CF2Oxe2x80x94, xe2x80x94CFClCF2CF2Oxe2x80x94 or xe2x80x94CHFCF2CF2Oxe2x80x94 and repeating units represented by xe2x80x94CCl2CF2CF2Oxe2x80x94 or xe2x80x94CHClCF2CF2Oxe2x80x94 and is composed of at least one repeating unit selected from xe2x80x94CF2CF2CF2Oxe2x80x94, xe2x80x94CFClCF2CF2Oxe2x80x94, xe2x80x94CHFCF2CF2Oxe2x80x94, xe2x80x94CCl2CF2CF2Oxe2x80x94, xe2x80x94CHClCF2CF2Oxe2x80x94 and xe2x80x94CH2CF2CF2Oxe2x80x94, the total of the repeating units (degree of polymerization) being 2 to 200 (this polymer is described in Japanese Unexamined Patent Publication No. 113616/1986).
Specific examples thereof include:
F(CHClCF2CF2O)nCHClCF3 (n is 5 on an average);
F(CCl2CF2CF2O)nCCl2CF3 (n is 5 on an average);
F(CCl2CF2CF2O)nCCl2CF2Cl (n is 25 on an average);
CCl2FCF2CF2OCCl2CF2CF2OCCl2CF3;
F(CClxFyCF2CF2O)nCClxFyCF3 (n is 5 on an average, x+y=2, x:y=1:4);
F(CF2CF2CF2O)x(CClFCF2CF2O)yxe2x80x94CF2CF2COF (x+y is 20 on an average, x:y=2:1, x number of units and y number of units are arranged in a random order); and
F(CF2CF2CF2O)x(CClFCF2CF2O)yCF2CF3 (x+y is 20 on an average, x:y=2:1, x number of units and y number of units are arranged in a random order).
(d) A polymer whose main portion (portion except for terminal groups) is composed of repeating units of xe2x80x94CF(CF3)CF2Oxe2x80x94, the total of the repeating units of hexafluoro-1,2-epoxypropane (degree of polymerization) being 10 to 100.
Specific examples thereof include:
F[CF(CF3)CF2O]nCHFCF3 (n is 50 on an average) (commercially available, for example, under the trade mark xe2x80x9cKrytox 143ADxe2x80x9d).
(e) A polymer whose main portion (portion except for terminal groups) is composed of 4 to 50 repeating units of xe2x80x94CF(CF3)CF2Oxe2x80x94 and 4 to 50 repeating units of xe2x80x94CF2Oxe2x80x94, the total of the repeated units of hexafluoro-1,2-epoxypropane and difluorocarbenoxy being 8 to 100.
Specific examples thereof include:
F[CF(CF3)CF2O]n(CF2O)nCF3 (n is 15 on an average, m is 6 on an average)(commercially available, for example, under the trade mark xe2x80x9cFomblin Y25xe2x80x9d).
(f) A polymer whose main portion (portion except for terminal groups) is composed of repeating units of xe2x80x94CF2CF2Oxe2x80x94, the total of the repeated units of tetrafluoroethane (degree of polymerization) being 7 to 100.
Specific examples include:
F(CF2CF2O)nCF3 (n is 25 on an average).
II. Fluorochloroolefin telomers include, for example, the following compound (g).
(g) A telomer whose main portion (portion except for terminal groups) is composed of repeating units of xe2x80x94CF2CFClxe2x80x94, the total of the repeating units of chlorotrifluoroethane (degree of telomerization) being 3 to 20.
Specific examples thereof include:
Cl(CF2CFCl)nCl (n is 6 on an average).
III. Fluoroolefin telomers include, for example, the following compound (h).
(h) A telomer whose main portion (portion other than terminal groups) is composed of 2 to 50 repeating units of xe2x80x94CF2CF2xe2x80x94, the total of the repeating units of tetrafluoroethylene (degree of telomerization) being 2 to 50.
Specific examples thereof include:
H(CF2CF2)nCF3 (n is 6 on an average), [(CF3)2CF(CF2)n]2 (n is 3.5 on an average), and Cl(CF2CF2)nCHF2 (n is 6 on an average).
IV. Fluoroalkanes include, for example, the following compounds:
(CF3)2CF(CF2)4CF(CF3)2 (b.p. 207xc2x0 C.),
(3) Polymer Prepared Using as a Monomer Component a Compound Having at Least one Fluorine-containing Group Selected from Polyfluoroalkyl Groups and Polyfluoroalkenyl Groups.
The polymer prepared using as a monomer component a compound having at least one fluorine-containing group selected from polyfluoroalkyl groups and polyfluoroalkenyl groups includes, for example, the following polymers:
(A) A copolymer of at least one fluorine-containing monomer selected from polyfluoroalkyl-containing (meth)acrylic esters, polyfluoroalkenyl-containing (meth)acrylic esters, polyfluoroalkyl-containing vinyl compounds and polyfluoroalkenyl-containing vinyl compounds, and another monomer copolymerizable therewith, the proportion of the fluorine-containing monomer being 20-95 parts by weight, preferably 30-90 parts by weight, based on 100 parts by weight of the total monomer component.
(B) A polymer of at least one fluorine-containing monomer selected from polyfluoroalkyl-containing epoxy monomers and polyfluoroalkenyl-containing epoxy monomers, or a copolymer of the fluorine-containing monomer and another monomer copolymerizable therewith, the proportion of the fluorine-containing monomer being 20-100 parts by weight, preferably 30-90 parts by weight, based on 100 parts by weight of the total monomer component.
The polymers (A) and (B) may be used singly or in combination of two or more.
The terms xe2x80x9cpolyfluoroalkylxe2x80x9d and xe2x80x9cpolyfluoroalkenylxe2x80x9d are used herein to refer to alkyl groups containing at least two fluorine atoms, and alkenyl groups containing at least two fluorine atoms, respectively. Preferably, each of the alkyl group and alkenyl group is a straight or branched chain group having 3 to 21 carbon atoms.
When the proportion of the fluorine-containing monomer in the copolymer (A) or (B) is lower than 20 parts by weight, it tends to be difficult to have high performance characteristics such as low surface energy, non-adhesion (mold releasability), water repellency and oil repellency.
First, the polymer (A) will be described below in detail.
Of the monomer components, polyfluoroalkyl-containing (meth)acrylic esters and polyfluoroalkenyl-containing (meth)acrylic esters include, for example, the following compounds:
wherein R5 is H or CH3 and Rf is a straight or branched chain polyfluroalkyl or polyfluoroalkenyl group having 3 to 21 carbon atoms.
Specific examples include perfluorooctylethyl acrylate, 2-perflourooctyl-1-methylethyl acrylate, 2-(N-ethylperfluorooctasulfonamide)ethyl acrylate.
Polyfluoroalkyl-containing vinyl compounds and polyfluoroalkenyl-containing vinyl compounds include, for example, the following compounds:
wherein R5 and Rf are as defined above.
Specific examples include perfluorooctylethylene, perfluorooctyloxyphenyl ethylene and the like. The compounds may be used in combination of two or more.
Rf represents a straight or branched chain polyfluoroalkyl or polyfluoroalkenyl group having 3 to 21 carbon atoms, preferably 4 to 16 carbon atoms. Usually selected as Rf is a one having perfluoroalkyl in the terminal region. Also usable are those containing hydrogen or chlorine in the terminal region or those containing oxypolyfluoroalkylene.
Polyfluoroalkyl-free monomers or polyfluoroalkenyl-free monomers may be used in addition to at least one fluorine-containing monomer selected from polyfluoroalkyl-containing (meth)acrylic esters, polyfluoroalkenyl-containing (meth)acrylic esters, polyfluoroalkyl-containing vinyl compounds and polyfluoroalkenyl-containing vinyl compounds.
Examples of polyfluoroalkyl-free monomers and polyfluoroalkenyl-free monomers include compounds having a radically reactive unsaturated bond. Specific examples include methacrylic or acrylic acids and esters thereof represented by the formulas
wherein R5 is as defined above and R6 is H or CbH2b+1 (wherein b is an integer of 1 to 23), and a is an integer of 1 to 30; for example, stearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl acrylate, polyethylene glycol mono(meth)acrylate, glycidyl (meth)acrylate, polyethyleneglycol di(meth)acrylate and the like.
Examples of polyfluoroalkyl-free monomers and polyfluoroalkenyl-free monomers further include monomers represented by the formulas
wherein R5 and R6 are as defined above. Specific examples include amide derivatives of (meth)acrylic acids; vinyl chloride, vinylidine chloride and like halogen-containing vinyl monomers; vinyl acetate, dialkyl esters of maleic acid and vinyl alcohols. Also usable are ethylene, vinylalkylether, maleic anhydride, styrene, xcex1-methylstyrene, p-methylstyrene, acrylonitrile, butadiene, isoprene, chloroprene, methyl vinyl ketone, ester derivatives of (meth)acrylic acid containing xe2x80x94NHCOOxe2x80x94, and the like.
The polymer (A) can be prepared by solution polymerization or emulsion polymerization using the monomer component.
Preferably, the proportion of the monomer component is 0.5 to 50%, particularly 1.0 to 50%, further more preferably 5 to 45%, based on the total weight of the monomer component and polymerization solvent. When the proportion of the monomer component is lower than 0.5%, the yield of polymer obtained in each polymerization run will decrease, thus being economically disadvantageous. When the proportion is higher than 50%, the polymerization system tends to gel readily, whereby the continuation of the reaction becomes difficult.
The solution polymerization is carried out usually using a polymerization initiator, preferably at temperatures of 20xc2x0 C. to 200xc2x0 C., particularly 30xc2x0 C. to 150xc2x0 C., further more preferably 40xc2x0 C. to 130xc2x0 C., optionally using a pressurized vessel such as an autoclave. When the polymerization temperature is lower than 20xc2x0 C., more monomers tend to remain unreacted. A polymerization temperature of higher than 200xc2x0 C. raises the internal pressure of the autoclave too highly, whereby the manufacturing in such a device will be difficult. The reaction is usually carried out for about 1 to about 20 hours, preferably about 2 to about 15 hours, more preferably about 3 to about 10 hours, although the reaction time may vary depending on the reaction temperature.
Useful polymerization solvents include water and a wide variety of organic solvents. Preferred solvents are the above-mentioned halogen-containing solvents, particularly bromine-containing solvents.
Useful polymerization initiators include, for example, organic peroxides, azo compounds including azobis compounds, and persulfates. Also usable are ionizing radiations such as gamma-ray.
For example, when a vinyl compound is used as a monomer component, solution polymerization can be carried out by known methods for polymerization of vinyl compounds. The polymerization may be carried out, for example, in a vessel equipped with a stirrer and a means for heating or cooling from the outside. More specifically, solution polymerization can be carried out, for example, in the following manner.
A monomer component is added to a polymerization solvent in such an amount that the proportion of the monomer component is 0.5 to 50 wt. %, based on the total weight of the monomer component and the polymerization solvent. The solution containing the monomer component in the polymerization solvent is adjusted to a temperature of 40-150xc2x0 C. and the polymerization is carried out in the presence of a polymerization initiator. When a vinyl compound is used as a monomer component, the polymerization initiator may be any known initiator for polymerization of unsaturated vinyl compounds. Usually used are peroxides and azo compounds that are readily soluble in solvents. Examples of peroxides include benzoyl peroxide, lauroyl peroxide and like acyl peroxides; t-butyl perbenzoate and like organic peresters; di-t-butyl peroxide and like dialkyl peroxides. Examples of azo compounds include azobis(isobutyronitrile) and azobis (2,4-dimethyl valeronitrile). The polymerization initiator is usually used in a proportion of about 0.1 to 2%, relative to the weight of the monomer component.
The molecular weight of the polymer may be controlled by adjustment of the initiator alone or other conditions. When the control achieved thereby is insufficient, a small amount of a chain transfer agent such as alkane(C1-C12) thiol may be added.
Preferably, the polymer obtained has a number average molecular weight of 1,000 to 100,000, particularly, 5,000 to 70,000, further more preferably 10,000 to 50,000. When the molecular weight is less than 1,000, the polymer will have insufficient properties in respect of low surface energy, non-adhesion (mold releasability), water repellency and oil repellency. When the molecular weight is more than 100,000, it tends to be difficult to maintain good storage stability.
The polymer (B) will be described.
The polymer (B) includes, for example, homopolymers of a fluorine-containing compound represented by the formula
(wherein Rf is a C3-21 straight or branched chain polyfluoroalkyl or polyfluoroalkenyl group, and c is an integer of 1 to 3); and copolymers of the fluorine-containing compound and a monomer copolymerizable therewith.
Specific examples of the fluorine-containing compounds of formula (7) are shown below.
The monomer copolymerizable with the fluorine-containing compounds of formula (7) includes, for example, cyclic anhydrides, cyclic esters, cyclic ethers, cyclic formals, epoxides and the like.
The cyclic anhydride is a five-membered cyclic compound formed by removing water from two carboxyl groups which are linked to two carbon atoms adjacent to each other. Specific examples include succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, 1,2-cyclohexanedicarboxylic anhydride, tetrahydrophthalic anhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2-cyclobutane dicarboxylic anhydride, endic anhydride, 1,2-naphthalene dicarboxylic anhydride, 2,3-naphthalene dicarboxylic anhydride, and substituted products thereof.
Specific examples of cyclic esters include xcex2-propiolactone, xcex3-butyrolactone, xcex4-valerolactone, xcex5-caprolactone and perfluoro-xcex3-butyrolactone.
Specific examples of cyclic ethers include oxetane, tetrahydrofuran, tetrahydropyran, 3,3-bis(chloromethyl)oxetane and perfluorooxetane.
Specific examples of cyclic formals include 1,3-dioxolane, trioxane, tetraoxane, 1,3,6-trioxocan and 1,3,5-trioxocan.
Specific examples of epoxides include ethylene oxide, propylene oxide, epichlorohydrin, perfluoropropylene oxide, isobutylene oxide, butadiene oxide, styrene oxide, methyl glycidyl ether and allyl glycidyl ether.
A homopolymer of the fluorine-containing compound or a copolymer of the fluorine-containing compound and the above exemplified monomer can be prepared by conducting usual polymerization reactions under suitable reaction conditions. For example, solution polymerization methods or bulk polymerization methods can be used. The polymerization reaction is carried out using, as a polymerization initiator, a catalyst for promoting a ring opening polymerization of epoxy, such as a cationic polymerization catalyst or a coordinated anionic polymerization catalyst, in the presence or absence of a solvent. Examples of cationic polymerization catalysts include boron trifluoride, boron trifluoride complex, tin tetrachloride, AlCl3, BF3(C2H5OH)2, metal halides, amines and the like. Examples of coordinated anionic polymerization catalysts include trialkylaluminum, dialkylzinc, phosphoric acid and the like. Useful solvents include trichlorotrifluoroethane, dimethylformamide, dimethoxyethane, n-hexane, ethers, ketones, cellosolves, carbitols and the like. The reaction temperature may be suitably selected in accordance with the reactivity of the starting monomer and is not particularly limited. It is usually preferable that the reaction temperature be in the range of about 0xc2x0 C. to about 150xc2x0 C.
In the case of producing a copolymer of the fluorine-containing compound of formula (7) and a monomer copolymerizable therewith, their proportions are not particularly limited and can be suitably selected. It is usually preferable that the fluorine-containing compound of formula (7) be used in a proportion of about 20 to about 100 parts by weight, based on 100 parts by weight of the total monomer component.
The polyether polymer or polyester polymer thus obtained is a transparent thermoplastic polymer. The resulting polymer usually has a glass transition point of about xe2x88x9210xc2x0 C. to about 200xc2x0 C., typically about 20xc2x0 C. to about 100xc2x0 C., although the glass transition point may vary depending on the kind and proportion of the monomer used. The polymer preferably has a number average molecular weight of about 2,000 to about 50,000, more preferably about 2,000 to 30,000.
In the below, (i) silicone compounds and (ii) waxes which are optionally used in the present invention will be described.
(i) Silicone Compound:
Examples of silicone compounds (i) include silicone oils, silicone resins, ladder polymers of organosilsesquioxanes. The compounds may be used singly or in combination of two or more.
Preferred silicone oils and silicone resins are, for example, usual polysiloxanes which are liquid or semi-solid at room temperature, or substituted polysiloxanes having a substituent such as C1-5 alkyl, C1-5 fluoroalkyl or phenyl. Generally speaking, compounds with low viscosity have a low friction coefficient, thus being preferred.
Examples of ladder polymers of organosilsesquioxanes are addition polymers of a hypothetical monomer represented by R7SiO1.5 (organosilsesquioxane), which have a ladder-shaped regular skeleton structure represented by the formula
wherein R7 is methyl or phenyl; part of the silicon atoms may be substituted by two hydroxyl groups provided, however, that the hydroxyl-disubstituted silicon atoms are not be very close to each other. In the case that two or more silicon atoms are substituted by two hydroxyl groups, it is preferable that at least one xe2x80x94Oxe2x80x94Sixe2x80x94Oxe2x80x94 bond be interposed between the substituted silicon atoms. The ladder polymer is usually prepared by a method comprising hydrolyzing one ore more species selected from trifunctional organosilanes such as methyl trichlorosilane, phenyl trichlorosilane, methyl triethoxysilane, phenyl triethoxysilane and the like, followed by polycondensation and equilibration of the hydrolysis product, optionally further followed by polycondensation.
Strictly defined, the ladder polymer of organosilsesquioxane is a polymer formed by chainwise or cyclic linking of one or more species selected from organosilsesquioxane oligomers represented by the formula
wherein the R8s are the same substituent and represent hydrogen, C1-6 alkyl, cyclohexyl, C2-6 alkenyl or phenyl, and d is an integer of 2 to 6). The degree of polymerization of the ladder polymer is about 2 to about 200, based on a repeating unit of
Ten percent or less of silicon atoms may be substituted by two hydroxyl groups but the substituted silicon atoms should not be very close to each other. When the ladder polymer is a chain polymer, halogen atom such as chlorine, C1-6 alkoxy, acetoxy or hydroxyl is bonded to terminal silicon atom. At the O-terminal, correspondingly to the Si-terminal, oxygen atom is substituted by halogen atom, or C1-6 alkyl group, acetoxy group or hydrogen atom is bonded.
Ladder polymers of organosilsesquioxane are known and can be prepared in accordance with the methods described in Encyclopedia of Polymer Science and Technology, Vol.12, pp.500-501, 1970, Japanese Examined Patent Publication No. 15989/1965, Japanese Unexamined Patent Publication No. 5826/1981, etc. The ladder polymers useful in the present invention are not limited to those prepared by such methods.
Specific examples of organosilsesquioxanes are shown below.
wherein the methyl to phenyl ratio is 2:1 and these groups are not necessarily at the positions shown above.
wherein the methyl to phenyl ratio is 1:4 and these groups are not necessarily at the positions shown above.
The above compounds (I), (II), (III), (IV) and (V) are commercially available under the trademarks xe2x80x9cGR100xe2x80x9d, xe2x80x9cGR150xe2x80x9d, xe2x80x9cGR650xe2x80x9d, xe2x80x9cGR908xe2x80x9d and xe2x80x9cGR950xe2x80x9d respectively (manufactured by Owens-Illinois Closure Inc., U.S.A.).
(ii) Wax
Waxes (ii) usable in the present invention are waxes in a broad sense, including not only vegetable or animal waxes used from old times but also mineral or synthetic waxes such as paraffin waxes. Examples of waxes include vegetable waxes of fatty acid esters such as carnauba wax and candela wax; mineral waxes such as polyethylene wax, microcrystalline wax and FT wax; animal waxes such as wool wax and beewax; and so on. The waxes may be used singly or in combination of two or more.
The surface treatment composition of the present invention is formed by dissolving the above-mentioned surface treatment component in a solvent component. If necessary, rust-preventive agents, antistatic agents, antibacterial agents, fungicides and the like may be added in accordance with the intended purpose.
The surface treatment composition of the present invention is a surface treatment agent used for purposes other than a water-repellent and an oil-repellent. The surface treatment composition finds applications, for example, as mold release agents applied to a metal mold for resin or rubber molding; resin adhesion inhibitors for lead wires of condensers or the like; flux barrier agents; anti-adhesion agents applied to various substrates such as metals, resins, rubbers, cloths, paper, wood, glass, metal oxide and pottery; antiblocking agents; rear surface treatment agents; antitacking agents; electric wire stripping agents; and lubricants. The composition is particularly suitable for mold release agents, resin adhesion inhibitors and anti-adhesion agents.
The method of using the surface treatment composition of the invention is not particularly limited. A suitable method can be selected in accordance with the article to be treated, etc. The desired surface treatment can be carried out, for example, by a method comprising immersing the article in the surface treatment composition, followed by drying, or a method comprising coating the surface of the article with the surface treatment composition, followed by drying.
The surface treatment composition of the invention may be used, for example, in the form of an aerosol containing a propellant. Preferred propellants include C1-2 fluoroalkane, C1-2 chlorofluoroalkane, LPG gas, dimethylether, nitrogen gas, carbon dioxide gas and the like. Typical examples of C1-2 fluoroalkane and C1-2 chlorofluoroalkane are dichlorodifluoromethane, trichlorotrifluoromethane, chlorodifluoromethane, chlorodifluoroethane, dichlorotrifluoroethane, tetrafluoroethane, and mixtures of at least two of these compounds. The propellent is preferably used in an amount that is between 0.05 and 2 times the total weight of the surface treatment composition including the solvent.
When used as an aerosol, the surface treatment composition and the propellent are usually contained in xe2x80x9ca container having a mechanism for ejecting a liquid from the containerxe2x80x9d. Examples of such xe2x80x9ccontainers having a mechanism for ejecting a liquid from the containerxe2x80x9d include aerosol containers, spray containers and the like.
The fluorine-containing surface treatment composition of the invention is a surface treatment agent that is extremely unlikely to cause ozone layer depletion and global warming, the composition having excellent storage stability and excellent performance characteristics as a surface treatment agent and being highly safe due to the non-flammability or flame retardancy thereof.


A pixel includes a driving transistor, an organic light emitting diode, a first transistor, and the second transistor. The driving transistor includes a gate electrode coupled to a first node, a first electrode coupled to a second node, and a drain electrode coupled to a third node. The driving transistor controls an amount of drain-source current based on a level of a voltage applied to the first node. The first transistor is coupled between the second node and a data line, and turns on by a scan signal of a scan line. The second transistor is coupled between the first node and an initialization voltage line, and turns on by an initialization signal of an initialization line. The first and second transistors are turned on during a first period.

1. Field
One or more embodiments described herein relate to a display device and a method for driving a display device.
2. Description of the Related Art
A variety of flat panel displays have been developed. Examples include liquid crystal displays, plasma display panels, and organic light emitting displays. Among these, the organic light emitting display is driven at a low voltage, has a wide viewing angle, a quick response speed, and thin dimensions.
An organic light emitting display has a plurality of pixels arranged in matrix form. Each pixel includes a scan transistor and a driving transistor. The scan transistor provides a data voltage from a data line in response to a scan signal. The driving transistor adjusts the amount of the current supplied to an organic light emitting diode based on a voltage supplied to its gate electrode.

Organic light emitting display device and method for driving the same


Systems, methods, and computer-readable storage media for optimizing and reporting time spent by a user engaged in a session. The system first obtains data associated with a presentation of an item of content at a mobile device, the presentation being divided into multiple partitions. Based on the data, the system adjusts at least one respective length of time associated with the multiple partitions to yield at least one adjusted length of time, the at least one adjusted length of time reflecting estimated time of user engagement with content associated with at least one of the multiple partitions. The system then determines an amount of time spent by a user at the mobile device engaging in the presentation based on the at least one adjusted length of time and the multiple partitions.

Mobile advertising is widely used by advertisers to market their products via mobile devices. Given the widespread availability of mobile devices, mobile advertising can be an extremely effective way for advertisers to reach a wide mass of potential customers and induce numerous users to purchase their products. By targeting mobile users with effective mobile advertisements, advertisers can yield large financial returns from their mobile advertisements. Not surprisingly, many advertisers continuously measure the performance of their advertisements to understand how, if necessary, they can optimize their advertisements for a better performance.
Many metrics are currently available for advertisers to measure the performance of their advertisements. For example, advertisers can measure the ratio of conversions obtained through their advertisements. In addition, advertisers can typically measure the number of views of a particular advertisement, to estimate the number of users reached by the particular advertisement and advertisement medium used. Unfortunately, however, it is generally difficult for advertisers to compare different advertisements based on the number of views measured, particularly when the different advertisements have varying amounts of content. Moreover, advertisers are currently unable to accurately and effectively determine the user's time spent engaging in an advertisement, and thus are limited in their understanding of the effects and performance of their advertisements. Consequently, advertisers are greatly limited in their ability to optimize their advertisements. And without accurate information regarding the user's engagement in an advertisement, it is very difficult to prevent click fraud from publishers seeking to inflate the metrics for their applications, without actually showing the advertisements to real users.

Active time spent optimization and reporting


A touchpad device includes a capacitive touch pad and a near field communication antenna. The capacitive touch pad includes a plurality of input circuits and a plurality of output circuits. Each input circuit and each output circuit intersect and are arranged substantially perpendicular to each other, thereby forming a chessboard-like circuit. The near field communication antenna includes an antenna structure crosses at least part of the plurality of input circuits and at least part of the plurality of output circuits. The antenna structure is substantially not parallel to any one of the input circuits crossed by the antenna structure, and the near field communication antenna being substantially not parallel to any one of the output circuits crossed by the antenna structure.

Using touch control technique to operate portable electronic apparatus has become the main trend technique nowadays. Touch control input function is included in laptops, tablets, smart phones or GPS to execute correspondingly operations. Take the laptop as an example, usually a touch pad is disposed near the keyboard. The user can use the touch pad to execute touch control for replacing mouse or keyboard, so as to provide more intuitive and convenient operation.
Besides, Near Field Communication (NFC) technique is broadly applied for short distance transmission and communication between two apparatuses. For the user's requirements, some manufacturers have combined the NFC technique with the portable apparatus such as a laptop to provide more functions. It has to dispose a corresponding antenna structure and related parts for operating the NFC function, and thus enough space inside the portable apparatus has to be arranged. In the laptop, only the space of the base near the touch pad could be used for disposing the antenna structure and related parts, so that less space inside the laptop is available.

Portable electronic apparatus and complex touch module thereof


An emulsion coagulant for coagulating a tire puncture sealant containing emulsion particles includes a mineral which induces aggregation of the emulsion particles by one or both of weakening of surface charge of the emulsion particles and formation of hydrogen bond between the mineral and the emulsion particles, and a gelation agent. The emulsion coagulant enables easy recovery of the tire puncture sealant from a tire as well as easy disposal of the recovered sealant.

This invention relates to an emulsion coagulant.
Various tire puncture sealants for repairing a punctured tire are proposed. Exemplary such tire puncture sealants include those prepared by blending a natural rubber latex with an emulsion of a tackifier resin and an antifreezing agent (see, for example, JP 2004-035867 A and JP 3210863 B), and those prepared by using a synthetic rubber latex such as acrylonitrile-butadiene rubber (NBR) latex or styrene-butadiene rubber (SBR) latex (see, for example, JP 2005-170973 A and JP 2001-62934 A).
In general, such tire puncture sealant is injected into a tire through an air-charging inlet of the tire and air is charged to a predetermined tire pressure, after which the car is driven to allow the tire puncture sealant to reach the puncture; and the compression and the shear generated during the tire rotation and contact of the tire with the ground cause the aggregation of the rubber particles in the tire to thereby seal the puncture and enable continuation of the driving.
In the case of the tire repaired with the tire puncture sealant, the tire contains the tire puncture sealant remaining in the tire in liquid state, and the tire is removed from the automobile in such condition. Therefore, after separating the rim from the tire, the tire puncture sealant remaining in the tire is collected, for example, in a bottle.
However, the recovered tire puncture sealant cannot be discarded without further treatment because the tire puncture sealant recovered generally contains an antifreezing agent such as ethylene glycol.


An assembly for a turbomachine turbine includes at least one ring sector made of CMC material and a support casing including an upstream flange and a downstream flange between which each ring sector is disposed, each ring sector including a base that has a radially external face from which radially extend two lugs, the lugs of each ring sector being retained between the two flanges of the support casing by axial pins each engaged in one of the flanges of the ring support casing and in the lug of the ring sector facing said flange, the assembly further including, for each ring sector, at least one radial retaining pin screwed into the support casing and coming to radially bear against a lug of the at least one ring sector to retain it in position, and anti-rotation system for rotationally locking the radial retaining pin.

This invention relates to the general field of aeronautical turbomachines. However, this invention could also be applied to any other gas turbine engine.
Ceramic Matrix Composite, or CMC, materials are known for retaining their mechanical properties at high temperatures, which makes them able to be used for making hot structural parts.
In aeronautical gas turbine engines, the improvement of efficiency and the reduction of certain contaminant emissions mean that operation at ever higher temperatures is desired. In the case of all-metal turbine rings, it is necessary to cool all the parts of the assembly and in particular the turbine ring that is subject to very hot flows, typically greater than the temperature that can be withstood by the metallic material. This cooling has a significant impact on the performance of the engine since the cooling flow used is bled from the main flow of the engine. Furthermore, the use of metal for the turbine ring limits the possibilities for increasing the temperature at the level of the turbine, which could however make it possible to improve the performance of aeronautical engines.
Moreover, a metallic turbine ring assembly becomes distorted under the effect of the thermal flows, which modifies the plays at the level of the flow duct and, consequently, the performance of the turbine.
This is why the use of CMC for various hot parts of the engines has already been envisioned, especially as CMCs have the additional advantage of having a lower density than that of the heat-resistant metals conventionally used.
Thus, the production of sectors of turbine ring out of a single CMC part is particularly described in the document US 2012/0027572. The ring sectors include a base, the radially internal face of which is intended to delimit a gas duct of the turbomachine and a radially external face from which radially extend two lugs, the ends of which are retained between the two flanges of a metallic ring support structure.
The use of CMC ring sectors thus makes it possible to significantly reduce the ventilation needed for the cooling of the turbine ring. However, the CMC having different mechanical behavior from a metallic material, its integration and the way of positioning it within the turbine have had to be redesigned. Specifically, CMC does not withstand interference-fitted assembly (usually used for metallic rings) and its thermal expansion is lower than a metallic material. Thus, to solve this problem, it is known to retain the lugs of the ring sectors using axial pins each engaged in one of the clamps of the ring support structure.
However, this type of assembly has the drawback that a radial play remains in the holes of the ring sector lugs provided for the passage of the axial pins, this play being able to cause a radial movement of the ring within the turbine. However, such a movement directly manifests as a variation of the play at the blade tip, and therefore as a direct impact on the engine performance.

Assembly for a turbomachine turbine and associated turbomachine


A stationary tooth row is provided in a restricted member that is not displaced together with a steering wheel during tilt adjustment of a steering system. A movable tooth row is provided in a movable member that is displaced in a tilt direction) together with the steering wheel during tilt adjustment. The movable tooth row includes a first movable tooth and second movable teeth. A first curvature radius of a tooth tip of the first movable tooth is made smaller than a second curvature radius of a tooth tip of each of the second movable teeth to make a tooth depth of the first movable tooth greater than a tooth depth of each of the second movable teeth.

1. Field of the Invention
The invention relates to a steering system.
2. Description of the Related Art
A structure for preventing half-lock, for example, in a steering system in which tilt adjustment can be made has been proposed. With this structure, in the course of engaging first lock teeth with second lock teeth, a guide projection that projects from a tooth tip of at least one of the first lock teeth is engaged with the corresponding second lock teeth before the remaining first lock teeth are engaged with the corresponding second lock teeth, so that the first lock teeth and the second lock teeth are aligned with each other as a whole. In this way, occurrence of half-lock is restricted. See Japanese Patent Application Publication No. 2010-264870 (JP 2010-264870 A), for example.
Japanese Patent Application Publication No. 2008-81026 (JP 2008-81026 A) describes a lock structure using engagement of teeth, in which the height of a specific tooth out of the teeth is made higher than that of the remaining teeth and the pressure angle of the specific tooth is made smaller than that of the remaining teeth.
In the structure described in JP 2010-264870 A, the guide projection that projects from the tooth tip has an insufficient strength and is not formed with ease. This exerts disadvantageous effect on the manufacturing. In the structure described in JP 2008-81026 A, the pressure angle of at least one of the teeth is made different from that of the remaining teeth. This makes the manufacturing difficult.


To provide a technology capable of promoting property of a thin film transistor formed on a glass substrate, a silicon oxide film 102 is formed on a glass substrate 101 and an amorphous silicon film 103 is formed thereon. A nickel acetate solution including nickel element that is a metal element promoting crystallization of silicon is coated and a water film 401 is formed. A state in which the nickel element is held in contact with the surface of the amorphous silicon film 103 is realized by performing spin drying. Uniform crystal growth is carried out as shown by arrow marks 104 by performing a heating treatment. An electrically inactive layer is formed by having nickel element having a high concentration which is present at front end portions of crystal growth react with an underlayer of the silicon oxide film 102. In this way the crystalline silicon film restraining the influence of nickel element can be provide.

There is known a technology of constituting a thin film transistor by using a silicon film formed on a glass substrate. The thin film transistor formed on a glass substrate is utilized in an active matrix type liquid crystal display device. A thin film transistor which has been reduced into practice currently uses an amorphous silicon film formed on a glass substrate by a plasma CVD (chemical vapor deposition) process.
However, the property of a thin film transistor obtained by an amorphous silicon film is poor and more improved property is currently required. Because of the poor property a thin film transistor of P-channel type cannot be manufactured using an amorphous silicon film (the property is considerably low compared with that of N-channel type and is out of practical use) and accordingly, it is not actually possible to constitute a CMOS circuit. Therefore, it is not possible to realize a structure using a CMOS circuit by a thin film transistor when an amorphous silicon film is used which considerably restricts its application.
A thermal annealing at 1000.degree. C. or more can be performed by using a single crystal wafer or a quartz substrate and therefore, it is possible to provide a crystalline silicon film having necessary properties by crystallizing the amorphous silicon film by a thermal annealing process. However, it is not possible to utilize a single crystal wafer wherein a visible light beam cannot be transmitted as a substrate constituting a liquid crystal device. Further, the quartz substrate is expensive which is inconvenient in view of production cost in expanding the area of the liquid crystal display device.
Under such a situation a technology in which an amorphous silicon film is formed on a glass substrate by a plasma CVD process or a low pressure CVD process and a crystalline silicon film is provided by some treatment, is required. As such a treatment a process by heating, a process by laser beam irradiation or the like has been known.
As a process by heating a method of crystallizing an amorphous silicon film by performing a heat treatment at a temperature of 600.degree. C. or more for several tens hours or more has been known. However, the strain point of a Corning 7059 glass substrate which is generally used frequently as a substrate for a liquid crystal display device is 593.degree. C. Deformation or wrinkle of the glass substrate becomes significant by exposing it under a temperature of 600.degree. C. or more for several tens hours which considerably influences on the manufacturing of devices. For example, the mask alignment becomes difficult by the deformation of the glass substrate. Especially, the problem becomes serious in expanding area. The problem is also recognized in case where other glass substrates are utilized.
Meanwhile, there is a superiority in adopting the process by laser beam irradiation in which the amorphous silicon film can be crystallized without causing thermal damage on a glass substrate. However, the utilization of a high power laser beam over a large area is difficult in view of the technology and production cost which lowers its practical use.
There is a technology described in Japanese Unexamined Patent Publication No. 232059/1994 as a technical means solving such a problem. The publication discloses a technology in which a metal element, (for example, nickel) promoting crystallization of silicon is held in contact with the surface of an amorphous silicon film formed on a glass substrate by a plasma processing and a crystalline silicon film is provided by performing a heating treatment at approximately 550.degree. C. for several hours.
With the heating treatment at 550.degree. C. for several hours the deformation or wrinkle of the substrate is not so serious even if Corning 7059 glass substrate is used. Therefore, it is an extremely useful method as a technology for providing a thin film transistor by using a crystalline silicon film. This process is very useful even if a glass substrate other than Corning 7059 glass substrate is used. However, conditions of the plasma processing are delicate in the technology disclosed in Japanese Unexamined Patent Publication No. 232059/1994 and in the actual reduction to practice a metal element having an amount more than necessary is introduced in the silicon film.
For example, when the concentration of nickel element finally remaining in the silicon film is 1.times.10.sup.19 atoms cm.sup.-3 or more, the influence of a nickel silicide component in the silicon film becomes significant and the property as a semiconductor is deteriorated. A means of strictly controlling an amount of doping a metal element is necessary to solve the problem. However, as mentioned above it is difficult to control the concentration of a metal element doped in the silicon film by the technology disclosed in Japanese Unexamined Patent Publication No. 232059/1994.

Semiconductor device and a method of manufacturing the same

Semiconductor Energy Laboratory Co., Ltd.


A web-enabled automation control module (ACM) includes an ACM central processing unit (CPU) and a web and file transfer system electrically connected to the ACM CPU, and embedded within the ACM. The system is configured to process hypertext transfer protocol (HTTP) requests from a network.

This invention relates generally to automation control modules (ACMs) and more particularly to management and control of ACMs.
Known ACM systems access ACM data using an input/output (I/O) module connected to a backplane on the ACM. The I/O module increases the cost of the system and uses additional space in the ACM system cabinet. In addition, if the backplane includes a plurality of modules, the I/O module may respond more slowly.
Known web-enabled ACM systems also provide pre-defined web pages that contain ACM data in a format determined by the manufacturer. Predefined web pages are inflexible and may be intolerable to many users. Furthermore, known ACM systems that include a web server use the ACM's central processing unit (CPU) to run the web server and the transmission control protocol (TCP)/internet protocol (IP) stack, thereby degrading performance of the CPU.

Methods and systems for management and control of an automation control module


A method for transmitting a multi-view program composed of a plurality of video streams in a digital broadcasting system includes generating information representing that the program is a multi-view program, information on a composition of the multi-view program and information on the plurality of physical channels through which the multi-view program is transmitted; and transmitting the multi-view program and the generated information through the plurality of physical channels.

1. Field of the Invention
Exemplary embodiments of the present invention relate to a method and apparatus for transmitting/receiving a multi-view program including a stereoscopic 3D program in a digital broadcasting system; and, more particularly, to a method and apparatus for transmitting/receiving a multi-view program composed of a plurality of video streams through a plurality of physical channels while maintaining service compatibility with a conventional 2D receiver.
2. Description of Related Art
In digital broadcasting systems, channels do not means physical radio frequency (RF) channels but mean virtual channels.
Conventional digital broadcasting systems have a structure in which data is transmitted through one or more logical virtual channels within one physical RF channel. For example, in a conventional two-dimensional (2D) digital broadcasting system, a program has one video stream, and the video stream is generally transmitted through virtual channels within one physical RF channel.
Meanwhile, since a stereoscopic 3D image expresses a 3D effect using a difference in visual angle between a left-view image (hereinafter, referred to as a 'left image') and a right-view image (hereinafter, referred to as a 'right image'), a stereoscopic 3D program has video streams for the left and right images to be transmitted. There are several methods for transmitting a video stream composed of left and right images. For example, a first method, as illustrated in FIG. 1A, is a method of decreasing the resolution of left and right images by a half with respect to width, combining the left and right images together as one image frame and then compressing the image frame, thereby transmitting the compressed image frame as one video stream. A second method is a method of decreasing the resolution of left and right images by a half with respect to length, combining the left and right images together as one image frame and then compressing the image frame, thereby transmitting the compressed image frame as one video stream. A third method, as illustrated in FIG. 1B, is a method of compressing left and right images for each frame and then transmitting the compressed left and right images as two video streams. For reference, in FIGS. 1A and 1B, "L" denotes a left image and "R" denotes a right image. In the first and second methods, an image having a resolution decreased by a half is transmitted, and therefore, deterioration of image quality occurs. However, in the third method, 3D watching is possible without deterioration of image quality. When comparing these methods in terms of transmission, the first and second methods have no difference from the conventional method of transmitting the 2D program. However, in the third method, two video streams are transmitted, and therefore, the quantity of data to be transmitted may exceed the capacity of one physical RF channel. In this case, there occurs a problem in that the two video streams are transmitted through one physical RF channel, like the conventional method of transmitting the 2D program.
If the method of transmitting video streams is not limited to a stereoscopic 3D program having two video streams to be transmitted but extended to a multi-view program having several video streams to be transmitted, it is almost impossible to transmit the multi-view program through one physical RF channel.
As described above, there is a limitation in transmitting a multi-view program including a stereoscopic 3D program through one physical RF channel, and therefore, the multi-view program is necessarily transmitted through two or more physical RF channels.
Since the capacity of the virtual channel through which the 2D program is transmitted does not exceed the capacity of the one physical RF channel, it is not generally considered in signaling information for receiving the conventional 2D program that a plurality of physical RF channels are received, and video streams transmitted through the respective physical channels are linked. Therefore, signaling information for receiving a virtual channel through which a multi-view program including a stereoscopic 3D program transmitted within a plurality of physical RF channels is necessarily contained in the signaling information for receiving the conventional 2D program.
Although the quantity of data of the 3D program having two video streams does not exceed the capacity of the one physical RF channel, the signaling information for receiving the virtual channel through which the multi-view program including the stereoscopic 3D program transmitted within the plurality of physical RF channels is necessarily provided even when watching the stereoscopic 3D program by transmitting a video stream corresponding to the right image through a separate physical RF channel, transmitting a video stream corresponding to the left image through the conventional 2D program channel and then liking video streams transmitted from a receiving stage to each of the channels so that the configuration of channels built to transmit the conventional 2D program is not changed.

3D image processing apparatus and method thereof using connection status and glass type selection icons

ELECTRONICS AND TELECOMMUNICATIONS RESEARCH INSTITUTE


It is an object of the present invention to provide a method for analyzing the interaction of a test substance with a ligand by analyzing a phenomenon whereby multiple test substances are simultaneously adsorbed to a ligand. The present invention provides a method for analyzing the interaction of test substances with a ligand by measuring the change in the surface plasmon resonance using a surface plasmon resonance measurement device wherein the above-described method comprises: supplying a solution containing two or more types of test substances after supplying a solution containing no test substances; measuring the change in the surface plasmon resonance; and analyzing the difference between the change in the surface plasmon resonance that is predicted from the adsorption rate constant (ka) and dissociation rate constant (kd) of each of the test substances that had previously been measured and the change in the surface plasmon resonance that has actually been measured.

In many cases, a compound used as a medicament interacts with a protein in a living body so as to exert its functions. For example, an enzyme inhibitor may bind to a target enzyme so as to inhibit the enzyme reaction, thereby changing biochemical reactions in a living body and expressing its pharmacological action. Thus, in order to search for a medicament, it is important to understand the binding strength of a protein with a candidate compound for such a medicament.
In recent years, as a means for analyzing the interactions of proteins with chemical substances, a surface plasmon resonance method has become a focus of attention. This method comprises immobilizing a protein on a metal surface such as gold, adding a chemical substance to the metal surface, and measuring the change in the surface plasmon resonance, so as to quantify the interaction of the protein with the chemical substance.
A test substance that is a chemical substance is adsorbed to a molecule interacting therewith (that is, a protein or the like immobilized on a metal surface) over time. The amount of the test substance adsorbed, that is, the change in SPR signals, is changed according to the following formula (1):dR/dt=ka·Cs·(Rmax−R)−kd·R   Formula (1)wherein, in the formula (1), R represents an SPR signal; Rmax represents the maximum SPR signal; ka represents an adsorption rate constant; kd represents a dissociation rate constant; and Cs represents a concentration of a test substance located adjacent to the metal surface.
Herein, the value of Cs is constant under ideal conditions where the liquid on the metal surface is constantly substituted with a fresh liquid. Thus, it is possible to determine ka and kd from the measurement results by solving a simple differential equation. A binding constant (KD) indicates the ratio between adsorption and dissociation, and it is represented by kd/ka.
Regarding such surface adsorption, when the n types of multiple compounds are adsorbed to a single adsorption site, the structure of which is not changed by adsorption, since such compounds are competitively adsorbed thereto, a change in SPR signals is represented by the following formula:
                                          ⅆ            R                                ⅆ            t                          =                  A          ·                                    ∑                              i                =                1                            n                                                                  (                                                                            Ka                      i                                        ·                                          Cs                      i                                        ·                                          (                                              1                        -                                                                              ∑                                                          i                              =                              1                                                        n                                                                                θ                            i                                                                                )                                                        -                                                            kd                      i                                        ·                                          θ                      i                                                                      )                            ·                              MW                i                                                                        Formula                                                            (          2          )                    wherein, in the formula (2), A represents a constant used for conversion from the adsorbed weight to SPR signals; and MWi, Csi, θi, kai, and kdi represent the molecular weight of compound i, the concentration thereof, the adsorption site share thereof, an adsorption rate constant, and a dissociation rate constant, respectively.
Herein, if ka and kd have previously been known, a change in SPR signals obtained when the n types of multiple compounds are adsorbed can be calculated by formula (2).
In such surface absorption, a change in SPR signals obtained when the n types of multiple compounds are adsorbed to different adsorption sites is represented by the following formula (3):
                                          ⅆ            R                                ⅆ            t                          =                              ∑                          i              =              1                        n                                          (                                                            Ka                  i                                ·                                  Cs                  i                                ·                                  (                                      R                                                                                max                        i                                                                                -                                                                              ∑                                                          i                              =                              1                                                        n                                                                                R                            i                                                                                )                                            -                                                kd                  i                                ·                                  R                  i                                                      )                                              Formula                                                            (          3          )                    wherein, in the formula (3), Ri represents a change in SPR signals of compound i; and Rmaxi represents the maximum adsorbed SPR signals of compound i.
Herein, if ka and kd have previously been known, a change in SPR signals obtained when the n types of multiple compounds are adsorbed can be calculated by formula (3).
It has been known that many physiologically active substances that become targets of medicaments change their structures when these substances bind to certain substances, so that they come to bind to other substances. For example, a single-stranded DNA forms a double strand together with DNA complementary thereto, so that it comes to bind to a certain type of DNA-recognition protein. In addition, it has also been known that a medicament acting on a certain type of enzyme (for example, cytokine, hormone, etc.) binds to a site of the enzyme known as an allosteric site that is different from a substrate recognition site, so that it changes the bindability of the substrate recognition site. Moreover, when a single protein constituting a complex protein is used by itself, it does not have the ability to recognize a physiologically active substance. However, when a plurality of such proteins form a complex, the complex protein can recognize a physiologically active substance.
Thus, for the development of medicaments, it is important to understand a phenomenon whereby multiple substances are simultaneously adsorbed to a ligand and to analyze a test substance by a means for evaluating such adsorption properties. However, the conventional adsorption analysis method only enables determination by competitive adsorption. For example, JP Patent Publication (Kokoku) No. 7-111435 B (1995) describes the analysis of multiple compounds to be analyzed binding to a sensor surface. Chem. Lett. 2002(3), 342 describes that a molecule to be analyzed is allowed to competitively bind to the surface, that it is compared with a case where no molecules to be analyzed are present, and that the concentration of the molecule to be analyzed is detected based on the fact that the change in SPR signals decreases as the above concentration decreases.
In order to search for medicaments, screening involving 1,000,000 or more types of compounds has commonly been conducted. It has been obvious that more experiments are required for the analysis of complex actions. Nevertheless, there have been no methods for differentiating competitive adsorption from a change in an adsorption site itself, so as to process a large amount of data rapidly. Accordingly, it is impossible to exhaustively study such complex actions under current circumstances.

This patent is subject to a terminal disclaimer.

Method for analyzing test substance by surface plasmon resonance analysis


A vehicle convoy management system includes a processor and a non-transitory computer readable memory configured to store a machine-readable instruction set. The machine-readable instruction set causes the vehicle convoy management system to: determine a first vehicle and a second vehicle form a convoy, delegate a first task to the first vehicle based on a first set of sensor resources of the first vehicle, delegate a second task to the second vehicle based on a second set of sensor resources of the second vehicle, where the first task is distinct from the second task, receive a first information generated in response to the first vehicle completing the first task with the first set of sensor resources, receive a second information generated in response to the second vehicle completing the second task, and transmit at least one of the first information or the second information to at least one vehicle.

Autonomous and non-autonomous vehicles increasingly include systems enabled with numerous sensor resources capable of supporting a driver with maneuvering a vehicle and/or automatically maneuvering a vehicle through an environment. As the level of sophistication increases with the demand for additional driver assistive systems and automatic control of a vehicle, the systems require an ever-increasing amount of computing resources within the vehicle. To handle the increased computational requirements of vehicle systems, some vehicles utilize off-board processing resources to complete analysis and computation of data.
Additionally, in situations where vehicles travel together in a convoy, information about an environment may be processed independently by each vehicle, thereby duplicating the collection of sensor data and processing of said sensor data.

Distributed data collection and processing among vehicle convoy members


Provided herein are processes for the preparation of 3-(5-amino-2-methyl-4-oxoquinazolin-3(4H)-yl)piperidine-2,6-dione, or an enantiomer or a mixture of enantiomers thereof; or a pharmaceutically acceptable salt thereof.

Many types of cancers are associated with new blood vessel formation, a process known as angiogenesis. Several mechanisms involved in tumor-induced angiogenesis have been elucidated. The most direct of these mechanisms is the secretion by the tumor cells of cytokines with angiogenic properties, including tumor necrosis factor α (TNF-α).
A variety of other diseases and disorders are also associated with or characterized by undesired angiogenesis. For example, enhanced or unregulated angiogenesis has been implicated in a number of diseases and medical conditions, including, but not limited to, ocular neovascular diseases, choroidal neovascular diseases, retina neovascular diseases, rubeosis (neovascularization of the angle), viral diseases, genetic diseases, inflammatory diseases, allergic diseases, and autoimmune diseases. Examples of such diseases and conditions include, but are not limited to, diabetic retinopathy, retinopathy of prematurity, corneal graft rejection, neovascular glaucoma, retrolental fibroplasia, arthritis, and proliferative vitreoretinopathy.
Certain 4-oxoquinazoline compounds, including 3-(5-amino-2-methyl-4-oxoquinazolin-3(4H)-yl)piperidine-2,6-dione, have been reported to be capable of controlling angiogenesis or inhibiting the production of certain cytokines, including TNF-α, and useful in the treatment and prevention of various diseases and conditions. See U.S. Pat. No. 7,635,700, the disclosure of which is incorporated herein by reference in its entirety.
A method for synthesizing 3-(5-amino-2-methyl-4-oxoquinazolin-3(4H)-yl)piperidine-2,6-dione has been described in U.S. Pat. No. 7,635,700. A need still exists for efficient and scalable processes for the preparation of 3-(5-amino-2-methyl-4-oxoquinazolin-3(4H)-yl)piperidine-2,6-dione, or an enantiomer or a mixture of enantiomers thereof; or a pharmaceutically acceptable salt, solvate, hydrate, or polymorph thereof.