text:
|N·mero de publicaci¾n
|Tipo de publicaci¾n
|N·mero de solicitud
|Fecha de publicaci¾n
|20 Jul 1993
|Fecha de presentaci¾n
|29 Abr 1991
|Fecha de prioridad
|29 Abr 1991
|N·mero de publicaci¾n
|James R. Erickson, David J. St. Clair
|Cesionario original
|Shell Oil Company
|Exportar cita
|BiBTeX, EndNote, RefMan
|Citas de patentes (32), Otras citas (10), Citada por (93), Clasificaciones (32), Eventos legales (11)
|Enlaces externos: USPTO, Cesi¾n de USPTO, Espacenet
(A--B--A).sub.n --Y.sub.r --(A.sub.q --B).sub.m
(A--B--A).sub.n -Y.sub.r --(A.sub.q --B).sub.m
This invention relates to viscous conjugated diene block copolymers. Further, the invention relates to crosslinked epoxidized polymers made from such block copolymers and adhesive compositions made therefrom.
Curing of adhesives based on conjugated diolefins and, optionally, vinyl aromatics has increased the range of service properties for such adhesives. Radiation curing and chemical curing of polymers to make such adhesives is known. This curing causes covalent crosslinking of the polymerized conjugated diolefins which is evidenced by a high gel content of the crosslinked polymer. Before crosslinking, the polymers are melt processable but after crosslinking, the gel cannot be processed as melts. Crosslinking therefore enhances solvent resistance and improves elevated temperature shear properties. Compositions can therefore be applied to a substrate in a melt and then crosslinked to form a superior adhesive. However, improvements in the adhesives could be made if the adhesives could be processed at lower temperatures and cured at lower dosages of radiation.
Further, the known curable adhesives which are based on vinyl aromatics and conjugated diolefins do not have particularly good long term heat, weather and ultraviolet stability due to the need to utilize unhydrogenated polymers. The known vinyl aromatic-conjugated diolefin based adhesives which are curable are unhydrogenated polymers. Hydrogenation is known to improve long term heat, weather and ultraviolet stability, but it removes the double bonds which are needed to effect the curing by radiation crosslinking. The requirement for this unsaturation is particularly evident when typical tackifiers are present in the compositions because their presence generally inhibits crosslinking of the polymer.
It is an object of the present invention to provide a block copolymer which can be modified so that it can be crosslinked, preferably by radiation, and which is easily melt processable before crosslinking but has a high gel content after crosslinking. Another object is to obtain a material which flows easily and does not have a strong elastic component prior to use. Further, it is an object of this invention to provide an adhesive composition which is based on this crosslinkable block copolymer.
The viscous block copolymers of the present invention have the formula
(A--B--A.sub.p).sub.n --Y.sub.r --(A.sub.q --B).sub.m
wherein Y is a coupling agent or coupling monomers, and wherein A and B are polymer blocks which may be homopolymer blocks of conjugated diolefin monomers, copolymer blocks of conjugated diolefin monomers or copolymer blocks of diolefin monomers and monoalkenyl aromatic hydrocarbon monomers. The A blocks have a greater number of tertiary unsaturation (TU) sites per unit of block mass than the B blocks, where a TU site is defined to be an aliphatic double bond (ADB) between a tertiary carbon atom and either a primary or secondary carbon atom. The A blocks have a molecular weight of from about 100 to about 3,000 and the B blocks have a molecular weight of from about 1000 to about 15,000. n is greater than 0, r is 0 or 1, m is greater than or equal to 0, and n+m ranges from 1 to 100. p and q may be 0 or 1. When either p or q or both are 1, extra TU sites are available in the interior of the polymer chain. By way of example, polymer block A could be polyisoprene having about 14.7 milliequivalents of residual ADB's per gram, all of which would be TU sites (14.7 Meq TU/g), and polymer block B could be polybutadiene having 18.5 milliequivalents of residual ADB's per gram, none of which would be TU sites (0 Meq TU/g).
The block copolymers of the present invention may be partially hydrogenated, epoxidized or both partially hydrogenated and epoxidized. When these polymers, are partially hydrogenated, it is recommended that they be hydrogenated to the extent that only from about 0.1 to about 3 milliequivalents of aliphatic double bonds per gram of polymer (0.1 to 3 Meq ADB/g) remain in the polymer. When these polymers are epoxidized, whether they are hydrogenated or not, it is preferred that the epoxidation take place only to the extent that about 0.1 to about 3 milliequivalents of epoxide per gram of polymer (0.1 to 3 Meq epoxide/g) are generated. Hence, the preferred epoxidized polymer has an epoxide equivalent weight of between about 10,000 and about 333. When both partial hydrogenation and epoxidation are used, it is preferred that the amount of aliphatic double bonds in the polymer should be reduced to about 0.5 Meq/g or less. The polymers may then be crosslinked through at least some of the epoxy functionality, preferably, by radiation.
Polymers containing ethylenic unsaturation can be prepared by copolymerizing one or more polyolefins, particularly a diolefin, by themselves or with one or more alkenyl aromatic hydrocarbon monomers. The copolymers may, of course, be random, tapered, block or a combination of these, as well as linear, star or radial.
The polymers containing ethylenic unsaturation or both aromatic and ethylenic unsaturation may be prepared using anionic initiators or polymerization catalysts. Such polymers may be prepared using bulk, solution or emulsion techniques. In any case, the polymer containing at least ethylenic unsaturation will, generally, be recovered as a solid such as a crumb, a powder, a pellet or the like, but it also may be recovered as a liquid such as in the present invention. Polymers containing ethylenic unsaturation and polymers containing both aromatic and ethylenic unsaturation are available commercially from several suppliers.
In general, when solution anionic techniques are used, copolymers of conjugated diolefins and alkenyl aromatic hydrocarbons are prepared by contacting the monomer or monomers to be polymerized simultaneously or sequentially with an anionic polymerization initiator such as group IA metals, their alkyls, amides, silanolates, napthalides, biphenyls or anthracenyl derivatives. It is preferred to use an organo alkali metal (such as sodium or potassium) compound in a suitable solvent at a temperature within the range from about -150░ C. to about 300░ C., preferably at a temperature within the range from about 0░ C. to about 100░ C. Particularly effective anionic polymerization initiators are organo lithium compounds having the general formula:
wherein R is an aliphatic, cycloaliphatic, aromatic or alkyl-substituted aromatic hydrocarbon radical having from 1 to about 20 carbon atoms and n is an integer of 1 to 4.
Conjugated diolefins which may be polymerized anionically include those conjugated diolefins containing from about 4 to about 24 carbon atoms such as 1,3-butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene and the like. Isoprene and butadiene are the preferred conjugated diene monomers for use in the present invention because of their low cost and ready availability. The conjugated diolefins which may be used in the present invention include monomers which do and monomers which do not form a polymer wherein the residual aliphatic double bonds are positioned between a tertiary carbon atom and another type of carbon atom. Examples of monomers that do provide TU sites after polymerization include isoprene (2-methyl-1,3-butadiene), 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1,3-butadiene (2-amyl-1,3-butadiene), 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, 2-nonyl-1,3-butadiene, 2-decyl-1,3-butadiene, 2-dodecyl-1,3-butadiene, 2-tetradecyl-1,3-butadiene, 2-hexadecyl-1,3-butadiene, 2-isoamyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2-methyl-1,3-heptadiene, 2-methyl-1,3-octadiene, 2-methyl-6-methylene-2,7-octadiene (myrcene), 2-methyl-1,3-nonyldiene, 2-methyl-1,3-decyldiene, and 2-methyl-1,3-dodecyldiene, as well as the 2-ethyl, 2-propyl, 2-butyl, 2-pentyl, 2-hexyl, 2-heptyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 2-tetradecyl, 2-hexadecyl, 2-isoamyl and 2-phenyl versions of all of these dienes. Those that do not form polymers wherein the residual aliphatic double bond are positioned between a tertiary carbon atom and another carbon atom include 1,3-butadiene, piperylene, 4,5-diethyl-1,3-octadiene and the like. Alkenyl aromatic hydrocarbons which may be copolymerized include vinyl aryl compounds such as styrene, various alkyl-substituted styrenes, alkoxy-substituted styrenes, vinyl naphthalene, alkyl-substituted vinyl napthalenes and the like.
In general, any of the solvents known in the prior art to be useful in the preparation of such polymers may be used. Suitable solvents, then, include straight- and branched chain hydrocarbons such as pentane, hexane, heptane, octane and the like, as well as, alkyl-substituted derivatives thereof; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and the like, as well as alkyl-substituted derivatives thereof; aromatic and alkyl-substituted derivatives thereof; aromatic and alkyl-substituted aromatic hydrocarbons such as benzene, napthalene, toluene, xylene and the like; hydrogenated aromatic hydrocarbons such as tetralin, decalin and the like; linear and cyclic ethers such as methyl ether, methylethyl ether, diethyl ether, tetrahydrofuran and the like.
More specifically, the polymers of the present invention are made by the anionic polymerization of conjugated diene monomers and alkenyl aromatic hydrocarbon monomers in a hydrocarbon solvent at a temperature between 0░ and 100░ C. using an alkyl lithium initiator. The living polymer chains are usually coupled by addition of divinyl monomer to form a star polymer. Additional monomers may or may not be added to grow more branches or to terminally functionalize the polymer and the living chain ends are quenched with a proton source.
As stated above, the molecular weight of the A blocks varies from about 100 to about 3,000 because this molecular weight provides an adequate number of carbon to carbon double bonds (TU sites) that resist hydrogenation and/or allow easier functionalization, such as epoxidation, and subsequent crosslinking. The molecular weight of the B blocks range from about 1,000 to about 15,000 to provide flexible, short polymeric chains that limit the viscosity and especially the elasticity of the final uncured polymer. The B blocks are relatively easy to hydrogenate and/or more difficult to functionalize, such as by epoxidation, and, hence, they tend to remain more flexible than the A blocks after crosslinking. Preferred versions of the block polymers of the present invention have A block molecular weights between about 30 and about 2,000, most preferably between about 600 and about 1,200, because the tighter ranges tend to provide the best balance of crosslinking site availability and viscosity control. The preferred B block molecular weight is between about 2,000 and about 10,000, most preferably between about 3,000 and 7,000, to minimize the polymer viscosity. In most cases, polymers, which fall within the preferred molecular weight ranges are viscous liquids at room or slightly elevated temperatures as compared to most commercial conjugated diene-monoalkenyl aromatic hydrocarbon block copolymers or the copolymers of U.S. Pat. No. 3,607,982, which are relatively high molecular weight viscoelastic solids.
Diblock molecular weights are conveniently measured by Gel Permeation Chromatography (GPC), where the PGC system has been appropriately calibrated. Polymers of known molecular weight are used to calibrate and these must be of the same molecular structure and chemical composition as the unknown diblock polymers that are to be measured. For anionically polymerized diblock polymers, diblock polymer is essentially monodisperse and it is both convenient and adequately descriptive to report the "peak" molecular weight of the narrow molecular weight distribution observed. Measurement of the true molecular weight of the final coupled star polymer is not as straightforward or as easy to make using GPC. This is because the star shaped molecules do not separate and elute through the packed GPC columns in the same manner as do the linear polymers used for the calibration, and, hence, the time of arrival at a UV or refractive index detector is not a good indicator of the molecular weight. A good method to use for a star polymer is to measure the weight average molecular weight by light scattering techniques. The sample is dissolved in a suitable solvent at a concentration less than 1.0 gram of sample per 100 milliliters of solvent and filtered using a syringe and porous membrane filters of less than 0.5 microns pore size directly into the light scattering cell. The light scattering measurements are performed as a function of scattering angle and of polymer concentration using standard procedures. The differential refractive index (DRI) of the sample is measured at the same wavelength and in the same solvent used for the light scattering. The following references are herein incorporated by reference:
1. Modern Size-Exclusion Liquid Chromatography, W. W. Yau, J. J. Kirkland, D. D. Bly, John Wiley & Sons, New York, N.Y., 1979.
2. Light Scattering from Polymer Solutions, M. B. Huglin, ed., Academic Press, New York, N.Y., 1972.
3. W. Kaye and A. J. Havlik, Applied Optics, 12, 541 (1973).
4. M. L. McConnell, American Laboratory, 63, May, 1978.
Referring to the formula set forth in the Summary of the Invention section, especially useful polymers within the scope of the present invention are those that have a value of n greater than about 4 and especially preferred polymers are those with a value of n greater than about 10. These polymers can be made especially reactive even when using low levels of epoxidation, such as about 0.1 to about 1.5 Meq epoxy/g, (polymers with epoxide equivalent weights of between about 10,000 and 667), because the number of epoxidized crosslinkable sites per polymer molecule is still relatively high. Also especially useful are polymers where the number of TU sites per unit of block mass on the A blocks exceeds that on the B blocks by a ratio of at least about 3:1, more preferably at least about 8:1, and most preferably by at leas about 20:1, because this allows the polymer to be crosslinked in local regions with relatively uncrosslinked regions spaced in between to provide flexibility if the polymer has been partially hydrogenated and epoxidized. When the end use for the polymer is for pressure sensitive adhesives or flexible coatings, it is often useful for the B block to contain little or no TU sites.
Diblock, linear, radial and symmetric and asymmetric star copolymers are encompassed by the (A--B--Ap)n --Yr --(Aq --B)m nomenclature. The following are illustrative examples.
(A--B)1 is a diblock polymer consisting of an A block and a B block and Y is absent. (A--B)1 YB1 is a diblock polymer consisting of an A block and double B block, where the two B blocks are separated only by a difunctional coupling agent Y. (A--B)1 B1 is a diblock polymer consisting of an A block and a double B block made by a second sequential addition of B block monomers. Y is absent. A double B block may have a combined molecular weight of up to 30,000. (A--B)2 Y is a linear A--B--Y--B--A polymer that was made by coupling and a (A--B)2 is a linear A--B--B--A polymer that was made by sequentially adding A, B, B, A block monomers. Y is absent. (A--B)4 Y is a symmetrical radial block copolymer where Y would usually be a tetrafunctional coupling agent. (A--B)2 YB2 is an asymmetrical radial block copolymer. (A--B)20 Y is a symmetrical star block copolymer and Y would be a small number of multifunctional monomer monomers such as those obtained when the coupling monomer is divinylbenzene (DVB). (A--B)3 YB17 is an asymmetrical star block copolymer. It can be conveniently made by initiating and polymerizing the A blocks and then adding more alkyl lithium to the reactor prior to adding the B-type monomers. Living A--B diblocks and B blocks will result that can be coupled with the appropriate agent, such as DVB. A statistical distribution of species will be made by this process, having the average (A--B)3 YB17 composition. (A--B)20 Y(A--B)20 is an asymmetrical star block copolymer prepared by coupling 20 A--B diblocks with a small number of coupling monomers, such as DVB monomer, and then adding A-type monomers followed by B-type monomers before quenching the living system with a proton source.
These are a wide variety of coupling agents that can be employed. Any polyfunctional coupling agent which contains at least two reactive sites can be employed. Examples of the types of compounds which can be used include the polyepoxides, polyisocyanates, polyimines, polyaldehydes, polyketones, polyanhydrides, polyesters, polyhalides, and the like. These compounds can contain two or more types of functional groups such as the combination of epoxy and aldehyde groups, isocyanate and halide groups, and the like. Many suitable types of these polyfunctional compounds have been described in U.S. Pat. Nos. 3,595,941; 3,468,972, 3,135,716; 3,078,254; 4,096,203 and 3,594,452 which are herein incorporated by reference. When the coupling agent has two reactive sites such as dibromoethane, the polymer will have a linear ABA structure. When the coupling agent has three or more reactive sites, such as silicon tetrachloride, the polymer will have a branched structure, such as (AB)n Y. Coupling monomers are coupling agents where several monomer units are necessary for every chain end to be coupled. Divinylbenzene is the most commonly used coupling monomer and results in star polymers.
Preparation of polymers which have controllable and predictable amounts of residual ethylenic unsaturation is disclosed in U.S. Pat. No. 4,879,349 which is herein incorporated by reference. The process disclosed therein includes copolymerizing substituted and unsubstituted conjugated diolefins and hydrogenating the copolymer under conditions which are effective to substantially hydrogenate the ethylenic unsaturation which is unsubstituted but leave the substituted ethylenic unsaturation substantially unhydrogenated. Partial hydrogenation utilizing the process described in this patent is preferred because of the excellent controllability of the amount of residual unsaturation. It is likely that better performance will be achieved when the catalyst disclosed in the patent is replaced by a titanium catalyst such as is disclosed in copending, commonly assigned, application Ser. No. 07/529,807, filed May 29, 1990, now U.S. Pat. No. 5,039,755 and entitled "Selective Hydrogenation of Conjugated Diolefin Polymers". Further, it is likely that better performance will be achieved if the polymerization process described in that copending application, utilizing termination of polymerization by hydrogen, is used herein.
When the polymers of the present invention are partially hydrogenated, they should be hydrogenated such that from about 0.1 to about 3 Meq/g of the aliphatic double bonds remain in the polymer because less than 0.1 does not give enough crosslinking and more than 3 gives too much without cost benefit. If unhydrogenated polymer or the partially hydrogenated polymer is to be epoxidized, then it is preferred that 0.1 to about 3 Meq/g of double bonds be consumed providing 0.1 to 3 Meq/g of epoxy functionality/ It is preferred that the extent of the epoxidation be from about 0.5 Meq/g to about 1.5 Meq/g because this is the best compromise between lower cost and having sufficient epoxy groups for good crosslinking.
Some of the advantages of relatively low levels of epoxidation are:
the manufacturing cost is lower because less epoxidizing agent is used;
can maintain the polymer as an elastic material because the crosslinking will not be dense;
the polymer will be more hydrophobic so water will be less of a problem;
the polymer can be formulated in conventional equipment; and
the polymer is less subject to undesirable post curing.
When both hydrogenation and epoxidation are used, the best reactive polymers are those in which the amount of aliphatic double bonds has been reduced to about 0.5 Meq/g or less, preferably 0.2 Meq/g or less. This provides polymers that have better ultraviolet, ozone, weather and long term heat aging resistance. The preferred method of making hydrogenated epoxidized polymers is to partially hydrogenate the polymer first and then follow with as complete as possible epoxidation of the residual double bonds as discussed in the following paragraph. However, the process may be carried out by epoxidizing the polymer and then hydrogenating it.
Partial hydrogenation is diene selective. Generally, the rate of hydrogenation is much greater for carbon-carbon double bonds in which neither of the carbons is tertiary than for carbon-carbon double bonds in which one of the carbons is a tertiary carbon (the TU sites). The rate of epoxidation of carbon-carbon double bonds is just the opposite. Tertiary carbons promote epoxidation with peroxyacids better than secondary carbons, which in turn are better than primary carbons. Thus, polymers of the present invention are especially suitable for the processes of partial hydrogenation or epoxidation and are especially suitable for the sequential use of both processes on the polymer. Use of partial hydrogenation alone on the present polymers preferentially leaves a greater number per unit of weight of residual diene double bonds in the A blocks of the polymers, which use of epoxidation alone produces a greater number of epoxidized diene monomers per unit of block weight in the A blocks than the B blocks. Generally, the partial hydrogenation is more selective to diene monomer type than epoxidation. For this reason, it is better to partially hydrogenate first and epoxidize last when both processes are used on the present polymers. The effectiveness of this approach will be seen in the examples.
An epoxidized polymer of the present invention can be further derivatized by a subsequent reaction either separately or in-situ to provide useful reactive elastomeric binders that have reactive functionality other than the epoxy group. Epoxy groups can be converted to hydroxyl functionality, capable of crosslinking with amino-formaldehyde resins or isocyanates, by reduction or reaction with water. Reaction with azide ion, reaction with cyanotrimethylsilane followed by reduction or reaction with dialkylaminosilanes, ammonia, or amines will give polymers containing both amino and hydroxyl functionality that can be used to enhance adhesion to cellulosic substrates or provide reactive sites for isocyanate cure. Reaction with amino or mercapto acids can be used to prepare polymers containing hydroxyl and carboxylic acid functionality, providing greater adhesion to metals or to basic polymers such as nylon. Reaction with mercaptosilanes can be used to prepare polymers containing the elements of coupling agents, providing excellent adhesion to glass. These functional groups may also be introduced in the form of protected functional groups by reaction of the epoxy with the appropriately functionalized organometallic reagent (lithium organocuprates, Grignard reagents). Hydroxyl and aldehyde functionality may also be introduced by hydroformylation. Reactions with acrylamides and acrylic acids will introduce sites for free radical grafting. Further neutralization of the carboxylic acid or amine-containing polymer with base or acid will give varying amounts of water dispersability, depending on the level of functionality and neutralization.
A partially hydrogenated or unhydrogenated, but not epoxidized, polymer of the present invention can be further derivatized as well. Such a polymer can be brominated such as by reacting it with a solution of HBr in acetic acid. It can be reacted with maleic anhydride to give anhydride groups. Amine-functionalized unhydrogenated or partially hydrogenated polymers can also be made from the polymers of the present invention and should be useful for coating applications.
Epoxidation of the base polymer can be effected by generally known methods such as by reaction with organic peracids which can be performed or formed in situ. Suitable preformed peracids include peracetic and perbenzoic acids. In situ formation may be accomplished by using hydrogen peroxide and a low molecular weight fatty acid such as formic acid. Alternatively, hydrogen peroxide in the presence of acetic acid or acetic anhydride and a cationic exchange region will form a peracid. The cationic exchange resin can optionally be replaced by a strong acid such as sulfuric acid or p-toluenesulfonic acid. The epoxidation reaction can be conducted directly in the polymerization cement (polymer solution in which the polymer was polymerized) or, alternatively, the polymer can be redissolved in an inert solvent such as toluene, benzene, hexane, cyclohexane, methylenechloride and the like and epoxidation conducted in this new solution or can be epoxidized neat. Epoxidation temperatures on the order of about 0░ to 130░ C. and reaction times from about 0.1 to 72 hours may be utilized. When employing hydrogen peroxide and acetic acid together with a catalyst such as sulfuric acid, the product can be a mixture of epoxide and hydroxy ester. The use of peroxide and formic acid in the presence of a strong acid may result in diolefin polymer blocks containing both epoxide and hydroxy ester groups. Due to these side reactions caused by the presence of an acid, it is preferable to carry out the epoxidation at the lowest possible temperature and for the shortest time consistent with the desired degree of epoxidation.
Epoxidation may also be accomplished by treatment of the polymer with hydroperoxides in the presence of transition metals such as Mo, W, Cr, V and Ag. Epoxy functionality may also be created by direct oxidation of ethylenic unsaturation by O2 in the presence of tetra cyanoethylene. A temperature of about 150░ C. and an oxygen partial pressure of about 58 atmospheres is suitable for this reaction.
The polymers of this invention are preferably cured by ultraviolet or electron beam radiation, but radiation curing utilizing a wide variety of electromagnetic wavelengths is feasible. Either ionizing radiation such as alpha, beta, gamma, X-rays and high energy electrons or non-ionizing radiation such as ultraviolet, visible, infrared, microwave and radio frequency may be used.
The most common sources of alpha, beta and gamma radiation are radioactive nuclei. A ionizing radiation source with commercial polymer crosslinking applications is gamma radiation that is produced from either cobalt-60 or cesium-137 radioactive nuclei. X-rays can be produced through deceleration of high speed electrons through the electric field of an atomic nucleus.
High voltage electron accelerators are preferred over gamma radiation and certain types of X-ray processing equipment. High energy electrons produced by machine acceleration, as opposed to radioisotopes, can be applied easily to industrial processes for the following reasons: easy on-off switching capability; less shielding is required than with gamma radiation; accelerator beam are directional and less penetrating than gamma or X-rays; and electron radiation provides high dose rates, i.e., maximum penetration per unit density of material, and is well suited for on-line, high speed processing applications. Commercially available high or low energy electron-processing equipment are the Dynamitron« device, dynacote, insulating-core transformer, linear accelerator, Van de Graaff accelerator, pelletron, laddertron and linear cathode. Manufacturers of high voltage electron-accelerator equipment are High Voltage Engineering Corporation, Burlington, Mass. and Radiation Dynamics, Inc., Westbury, N.Y. Manufacturers of low energy electron beam generating equipment include American International Technologies, Inc., of Torrance, Calif.; RPC Industries of Hayward, Calif.; and Energy Sciences of Wilmington, Mass.
Ultraviolet light sources may be based on the mercury-vapor arc. Mercury is enclosed in a quartz tube and a potential is applied to electrodes at either end of the tube. The electrodes can be of mercury, iron, tungsten or other metals. The pressure in the mercury-vapor lamp may be less than 1 atm to more than 10 atm. As the mercury pressure and lamp operating temperatures are increased, the radiation becomes more intense and the width of the emission lines increases. Other UV light sources include electrodeless lamps, Xenon lamps, pulsed Xenon lamps, Argon ion lasers and Excimer lasers.
Visible light sources can be obtained from high pressure mercury arcs by addition of rare gases or metal halides, which increase the number of emission lines in the 350-600 nm region of the spectrum. Fluorescent lamps, tungsten halide lamps and visible lasers may also be utilized.
The mechanism of the radiation crosslinking is believed to be generation of cations by removal of an electron from the polymer chain. The cation then readily reacts with an epoxy group, if an epoxy group is available. This reaction results in an ether crosslink between two polymer molecules and a new cation site on a polymer which formerly contained the epoxy functionality. The new cation will either propagate, forming another ether crosslink with another epoxy oxygen, or terminate by recapturing an electron.
The presence of water in the polymeric composition during the radiation crosslinking is very undesirable due to the tendency of water to terminate the crosslinking. The radiation curing is therefore generally more effective if the polymeric composition is at a temperature near or above the boiling point of water at the time of the radiation curing.
The amount of radiation necessary for high gel formation varies with the thickness of the polymeric mass being irradiated, the amount of epoxy functionality, the extent to which the epoxy functionality is concentrated in specific regions within the polymeric mass and the type of radiation utilized. When electron beam radiation is utilized, radiation doses of about 0.1 Mrads to about 10 Mrads are acceptable and from about 0.1 Mrads to about 5 Mrads are preferred because of equipment cost and possible damage to substrate material.
When using non-ionizing radiation it is necessary to employ a photoinitiator to initiate the crosslinking reaction. Useful photoinitiators include diaryliodonium, alkoxy-substituted diarylidonium, triarylsulfonium, dialkylphenacrylsulfonium, and dialkyl-4-hydrophenylsulfonium salts. The anions in these salts generally possess low nucleophilic character and include SbF6 -, BF4 -, PF6 - and AsF6 -. Specific examples include (4-octyloxyphenyl)-phenyl-iodonium hexafluoroantimonate, UVI-6990 (from Union Carbide), and FX-512 (3M Company). Bis(dodecylphenyl)iodonium hexafluoroantimonate, UVI-6974 (Union Carbide), is especially effective. The onium salts can be used alone or in conjunction with a photosensitizer to respond to long wave length UV and visible light. Examples of photosensitizers include thioxanthone, anthracene, perylene, pheothiazione, 1,2-benzathracene coronene, pyrene and tetracene. The photoinitiator and photosensitizer are chosen to be compatible with the polymer being crosslinked and the light source available.
Radiation induced cationic curing may also be done in combination with free radical curing. Free radical curing can be further enhanced by the addition of additional free radical photoinitiators and photosensitizers for them.
Reactive (radiation curable) diluents that can be added to the polymer include alcohols, vinyl ethers, epoxides, acrylate and methacrylate monomers, oligomers and polymers. They may also be blended with other diene-based polymers. Examples of epoxides include bis(2,3-epoxy cyclopentyl)ether (Union Carbide EP-205), vinyl cyclohexane dioxide, limonene dioxide, epoxidized soya and linseed oils and fatty acids.
The polymers may also be cured without the use of radiation by addition of a cationic initiator. Suitable initiators include the halides of tin, aluminum, zinc, boron, silicon, iron, titanium, magnesium and antimony, and the fluoroborates of many of these metals. BF3 complexes such as BF3 -ether and BF3 -amine are included. Also useful are strong Bronsted acids such as trifluoromethanesulfonic (triflic acid) and the salts of triflic acid such as FC-520 (3M Company). The cationic initiator is chosen to be compatible with the polymer being crosslinked, the method of application and cure temperature. The epoxy-containing polymers may also be crosslinked by the addition of multifunctional carboxylic acids and acid anhydrides and in general by the curing methods described in U.S. Pat. No. 3,970,608, which is incorporated by reference. Radiation crosslinking is preferred because reactive ingredients do not come in contact with warm adhesives.
The crosslinked materials of the present invention are useful in adhesives (including pressure sensitive adhesives, contact adhesives, laminating adhesives and assembly adhesives), sealants, coatings, films (such as those requiring heat and solvent resistance), etc. In adhesive applications, it may be necessary to add an adhesion promoting or tackifying resin that is compatible with the polymer. A common tackifying resin is a diene-olefin copolymer of piperylene and 2-methyl-2-butene having a softening point of about 95░ C. This resin is available commercially under the tradename Wingtack« 95 and is prepared by the cationic polymerization of 60% piperylene, 10% isoprene, 5% cyclopentadiene, 15% 2-methyl-2-butene and about 10% dimer, as taught in U.S. Pat. No. 3,577,398. Other tackifying resins, such as Piccotex« 120 resin, may be employed wherein the resinous copolymer comprises 20-80 weight percent of piperylene and 80-20 weight percent of 2-methyl-2-butene. The resins normally have softening points (ring and ball) between about 80░ C. and about 115░ C.
Other adhesion promoting resins which are also useful in the compositions of this invention include hydrogenated resins, esters of rosins, polyterpenes, terpenephenol resins and polymerized mixed olefins, lower softening point resins and liquid resins. An example of a liquid resin is Adtac« LV resin from Hercules. To obtain good thermo-oxidative and color stability, it is preferred that the tackifying resin be a saturated resin, e.g., a hydrogenated dicyclopentadiene resin such as Escorez« 5000 series resin made by Exxon or a hydrogenated polystyrene or polyalphamethylstyrene resin such as Regalrez« resin made by Hercules. The amount of adhesion promoting resin employed varies from about 10 to about 400 parts by weight per hundred parts rubber (phr), preferably from about 20 to about 350 phr. The selection of the particular tackifying agent is, in large part, dependent upon the specific polymer employed in the respective adhesive composition.
The adhesive composition of the instant invention may contain plasticizers, such as rubber extending plasticizers, or compounding oils or organic or inorganic pigments and dyes. Rubber compounding oils are well-known in the art and include both high saturates content oils and high aromatics content oils. Preferred plasticizers are highly saturated oils, e.g. Tufflo« 6056 and 6204 oil made by Arco and process oils, e.g. Shellflex« 371 oil made by Shell. The amounts of rubber compounding oil employed in the invention composition can vary from 0 to about 500 phr, preferably between about 0 to about 100 phr, and most preferably between about 0 and about 60 phr.
Optional components of the present invention are stabilizers which inhibit or retard heat degradation, oxidation, skin formation and color formation. Stabilizers are typically added to the commercially available compounds in order to protect the polymers against heat degradation and oxidation during the preparation, use and high temperature storage of the adhesive composition.
Combinations of primary and secondary antioxidants are preferred. Such combinations include sterically hindered phenolics with phosphites or thioethers, such as hydroxyphenylpropionates with aryl phosphates or thioethers, or amino phenols with aryl phosphates. Specific examples of useful antioxidant combinations include (3-3,5-di-t-butyl-4-hydroxyphenyl)propionate)methane (Irganox« 1010 from Ciba-Geigy) with tris(nonylphenyl)phosphite (Polygard« HR from Uniroyal), Irganox« 1010 with bis(2,4-di-t-t-butyl)pentaerythritol disphosphite (Ultranox« 626 from Borg-Warner), 4-((4,6-bis(octylthio)-s-triazin-2-yl)amino)-2,6-di-t-butylphenol (Irganox« 565) with Polygard« HR, and Irganox« 565 with Ultranox« 626.
Additional stabilizers known in the art may also be incorporated into the adhesive composition. These may be for protection during the life of the article against, for example, oxygen, ozone and ultra-violet radiation. However, these additional stabilizers should be compatible with the essential stabilizers mentioned hereinabove and their intended function as taught herein.
The adhesive compositions of the present invention are typically prepared by blending the components at an elevated temperature, preferably between about 50░ C. and about 200░ C., until a homogeneous blend is obtained, usually less than three (3) hours. Various methods of blending are known to the art and any method that produces a homogeneous blend is satisfactory. The resultant adhesives may then preferably be used in a wide variety of product assembly applications. Alternatively, the ingredients may be blended into a solvent.
The adhesive compositions of the present invention may be utilized as many different kinds of adhesives, for example, laminating adhesives, pressure sensitive adhesives, tie layers, hot melt adhesives, solvent borne adhesives and waterborne adhesives in which the water has been removed before curing. The adhesive can consist of simply the epoxidized polymer or, more commonly, a formulated composition containing a significant portion of the epoxidized polymer along with other known adhesive composition components. A preferred method of application will be hot melt application at a temperature around or above 100░ C. because hot melt application above 100░ C. minimizes the presence of water and other low molecular weight inhibitors of cationic polymerization. The adhesive can be heated before and after cure to further promote cure or post cure. Radiation cure of hot adhesive is believed to promote faster cure than radiation cure at lower temperatures.
Preferred uses of the present formulations are the preparation of pressure-sensitive adhesive tapes and the manufacture of labels. The pressure-sensitive adhesive tape comprises a flexible backing sheet and a layer of the adhesive composition of the instant invention coated on one major surface of the backing sheet. The backing sheet may be a plastic film, paper or any other suitable material and the tape may include various other layers or coatings, such as primers, release coatings and the like, which are used in the manufacture of pressure-sensitive adhesive tapes. Alternatively, when the amount of tackifying resin is zero, the compositions of the present invention may be used for adhesives that do not tear paper and molded goods and the like.
A (polyisoprene-polybutadiene)n divinylbenzene star polymer was prepared in cyclohexane containing a small amount of diethyl ether cosolvent by the well known anionic polymerization method. For about every one mole of active initiator (sec-butyl lithium), 4.5 moles of 1,3-isoprene, 65 moles of 1,3-butadiene and 3.8 moles of technical divinylbenzene were added and polymerized successively, and the polymer was terminated with methanol. The technical divinyl benzene was DVB-55 from Dow, which consists primarily of mixed isomers of divinylbenzene and ethylvinylbenzene. The molar ratios correspond to the given % by weight composition for the polymer.
______________________________________ weight %______________________________________ butyl group 1.3 polyisoprene 7.1 polybutadiene 80.4 DVB-55 mixture 11.2______________________________________
Therefore, a (A--B)n Y polymer had been produced where A was polyisoprene, B was polybutadiene, and Y was DVB. The peak diblock arm molecular weight, as determined by GPC, was about 3900. Thus, the polyisoprene block had a molecular weight of about 370 and consisted of one terminal butyl group and about 4 to 5 isoprene mers. The polybutadiene block had a molecular weight of about 3500 and consisted of about 65 butadiene mers. Thus, block A contained TU sites, about 12 Meq/g, while block B had no TU sites.
The above polymer solution of Example 1 was partially hydrogenated using a nickel-aluminum catalyst under conditions that will not hydrogenate aromatic double bonds but will preferentially hydrogenate aliphatic double bonds that are not TU sites, and the catalyst was made by the reaction of nickel octoate and triethylaluminum, and was used at 15 ppm nickel, on a solution basis, at a pressure of 700 psi. A portion of the polymer was dried. NMR analysis provided the following composition of residual double bonds.
______________________________________NMR Results Weight % Meq. ADB/g polymer______________________________________1,4 isoprene (intact) 3.5 0.513,4 isoprene (intact) 1.2 0.181,4 butadiene (intact) 1.2 0.221,2 butadiene (intact) 0.1 0.02other (hydrogenated mers 94.0DVB) 100.0 0.93______________________________________
Thus, the partially hydrogenated polymer had A blocks which each consisted of one butyl group, and on average, about 3 isoprene mers with their residual ADB intact and about 1.5 hydrogenated isoprene mers. The B blocks, on average, each contained about 1 butadiene mer with its ADB intact and about 64 hydrogenated butadiene mers. The weight average molecular weight, Mw, of the partially hydrogenated polymer was as measured by static light scattering. Dry polymer was dissolved in tetrahydrofuran and filtered through a 0.5 and a 0.2 micron filter. The analysis wavelength was 632.8 nm, the temperature was 25.0░ C. and the DRI was 0.0884. The Mw determined was 85,000. Dividing this Mw, less the DVB contribution, by the diblock peak molecular weight of about 3900 plus the small contribution due to hydrogenation, indicated that the star had about 19 diblock arms, n=19. Hydrogenation of the polymer increased its viscosity, but the viscosity of the partially hydrogenated polymer both neat and dissolved in toluene was still low.
______________________________________Neat Viscosity______________________________________Temperature, ░C. 60 80 100Viscosity, cps 37,000 14,000 5,700______________________________________Toluene Solution Viscosity______________________________________Solids, wt % 40 50 60Viscosity, cps 115 290 810(25░ C.)______________________________________
By way of comparison, the well known commercial hydrogenated polymers shown below are all viscoselastic solids at room temperature through 100░ C. and have the shown typical toluene solution viscosities at 25% solids and 25░ C.
______________________________________KRATON « G1650 8000 cpsKRATON « G1652 1350 cpsKRATON « G1657 4200 cps______________________________________
The above partially hydrogenated polymer in solution was epoxidized with a solution of peracetic acid from FMC Corp. After neutralization with base and water washing, the polymer solution was poured out into a shallow pan and dried to recover the neat polymer. The polymer was found to be slightly more viscous after epoxidation then before. The polymer was analyzed by NMR to determine the number and type of residual double bonds.
______________________________________NMR Results Weight % Meq. ADB/g polymers______________________________________1,4 isoprene (intact) 0.3 0.043,4 isoprene (intact) 0.6 0.091,4 butadiene (intact) 0.1 0.021,2 butadiene (intact) 0.0 0.00other (aliphatic, DVB) 99.0 100.0 0.15Meq/g for epoxide 0.70(from epoxide titration)______________________________________
Thus, the A blocks each contained, on average, about 0.6 isoprene mers with their residual ADB intact and each B block contained little or no mers with their residual ADB intact. Hence, it can be inferred that the average A blocks contained a butyl group, about 2.4 epoxidized isoprene mers, and about 1.4 hydrogenated isoprene mers, while the average B block contained about 1.0 epoxidized butadiene mer and about 64 hydrogenated butadiene mers. Overall, each polymer molecule contained about 66 epoxide groups and about 13 residual aliphatic double bonds.
The amount of epoxy was also measured by the direct titration with perchloric acid (0.1N) and quarternary ammonium halogenide (tetraethylammonium bromide) where the sample was dissolved in methylene chloride. Epoxy titration is described to Epoxy Resins Chemistry and Technology, edited by Clayton A. May and published in 1988 (p. 1065) which is herein incorporated by reference. This method indicated that each polymer molecule contained about 60 epoxide groups.
The polymer of Example 3 is a gooey, viscous liquid at room temperature that has little internal (cohesive) strength. However, it is very easy to either warm melt or solution apply the neat polymer or the compounded polymer as a thin film to a substrate. Upon crosslinking through the epoxide groups, the polymer gains considerable cohesive strength without becoming brittle or inflexible and can be used to make useful pressure sensitive adhesives having high temperature service properties and solvent resistance as shown below.
______________________________________PSA formula-tion 4A 4B 4C 4D 4E 4F______________________________________Polymer 99.2 74.4 49.6 99.7 74.8 49.9Regalrez « 0.0 24.8 49.6 0.0 24.9 49.81094Irganox « 0.3 0.3 0.3 0.3 0.3 0.31010FC-520 0.5 0.5 0.5 0.0 0.0 0.0 100.0 100.0 100.0 100.0 100.0 100.0______________________________________
Regalrez« 1094 resin is a hydrogenated high softening point tackifying resin from Hercules, Irganox« 1010 antioxidant is a phenolic antioxidant from Ciba-Geigy and FC-520 is a solution of a salt of triflic acid from 3M Company.
Formulations 4A-4C were dissolved in toluene and cast onto Mylar film and the solvent was allowed to evaporate. About 1.5 mil dry films of a gooey material were obtained. The films were placed in an oven and baked at 149░ C. for 20 minutes to convert the gooey, viscous films into useful pressure sensitive adhesives which have good cohesive strength. The polymer gel content of each of the films was measured by the test of reference which is described in the article "Experimental Thermoplastic Rubbers for Enhanced Radiation Crosslinking of Hot Melt PSA's" published in the May 1985 Hot Melt Symposium of TAPPI which is herein incorporated by reference. The results below show that the polymer crosslinks well.
______________________________________Formulation Polymer gel content, %______________________________________4A 864B 1004C 65______________________________________
Formulations 4D-4F, which have no FC-520 catalyst in them, were similarly dissolved and cast onto Mylar and dried. They were given a short bake to simulate being hot melt extruded and were then treated under a nitrogen blanket with electron beam radiation using 165 kev electrons. Without EB treatment the films remain a gooey liquid having no gel content or other desirable properties. However, upon EB treatment they formed useful pressure sensitive adhesives (PSA) which have good cohesive strength. The polymer gel content results given below were obtained.
______________________________________Formulation Polymer gel content, %Dose, Mrad 0 3 5 7______________________________________4D 1 57 95 1004E 1 53 69 784F 1 48 67 73______________________________________
The following results were obtained upon PSA testing of formulation 4B that was baked for 20 minutes at 149░ C. and formulation 4E that was EB cured with 5 Mrads. A commercial high temperature, high performance automotive grade masking tape, 3M No. 233, was run as a control.
______________________________________ 4B 4E 3M No. 233______________________________________95░ C. Holding Power to Mylar, >1000 >1000 621min (1 in * 1 in * 500 g)23░ C. Holding Power to Steel, >4000 >4000 >4000min (1 in * 1 in * 500 g)23░ C. Polyken Probe Tack, grams 760 520 34023░ C. 180░ Peel from Steel, pli 1.2 1.2 2.1(pounds per linear inch)______________________________________
This illustrates that formulations of the present invention have properties similar to or better than the high performance commercial product.
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|6 Nov 1995
|15 May 1996
|Shell Internationale Research Maatschappij B.V.
|Low viscosity adhesive compositions containing asymmetric radial polymers
|4 Nov 2004
|28 Oct 2009
|Henkel AG & Co. KGaA
|Sulfonium salt photoinitiators and their use
|4 Nov 2004
|28 Oct 2009
|Henkel AG & Co. KGaA
|Sulfonium salts as photoinitiators
|12 Sep 2006
|19 May 2010
|Dow Global Technologies Inc.
|Ethylene/ alpha-olefins compositions, articles made therefrom and methods for preparing the same
|15 May 1996
|21 Nov 1996
|Shell Internationale Research Maatschappij B.V.
|Concurrent epoxidation and catalyst residue extraction
|21 Mar 1997
|2 Oct 1997
|Shell Internationale Research Maatschappij B.V.
|High temperature, low viscosity thermoplastic elastomer block copolymer compositions
|16 Sep 1999
|6 Jul 2000
|3M Innovative Properties Company
|Electronic circuit device comprising an epoxy-modified aromatic vinyl-conjugated diene block copolymer
|12 Sep 2006
|22 Mar 2007
|Dow Global Technologies Inc.
|Automotive parts prepared from ethylene/alpha -olefins compositions
|12 Sep 2006
|22 Mar 2007
|Dow Global Technologies Inc.
|ETHYLENE/ α-OLEFINS COMPOSITIONS, ARTICLES MADE THEREFROM AND METHODS FOR PREPARING THE SAME
|31 Oct 2007
|15 May 2008
|Dow Global Technologies Inc.
|Polyurethane compositions and articles prepared therefrom, and methods for making the same
|23 Jun 2011
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|Dow Global Technologies Llc
|Polymer compositions
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|525/314, 525/338, 522/170, 525/383, 525/271, 525/387, 525/250
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text: Captain's Log, Stardate 5.21.2011. We've.......... been told, that today........ is suppose to be Rapture (Judgement Day)! This pridiction is from Harold Camping, an 89-year-old retired engineer-turned-oracle. Harold claims that today, May 21, 2011, Jesus would come back and take all of his Saints. Well, Mr. Camping.. you're wrong! For all Rapture survivors, check out this cool "I survived Rapture!" t-shirt site. http://raptureshmapture.com/

subset: commoncrawl


text:
Nasdaq has a fight on its hands after rival Borse Dubai launched a formal hostile takeover offer for Swedish stock exchange OMX.
Borse Dubai's all-cash SEK230 a share offer values OMX at SEK27.7bn (£2.02bn).
That is 17pc higher than Nasdaq's recommended cash-and-shares offer, which values each OMX share at SEK197. Nasdaq's offer has slipped with its share price from SEK208.1.
Borse Dubai, pitching its offer as a merger rather than a takeover, has built a sizeable stake in OMX. Last week it bought a 4.9pc stake, and also took out options on a further 23.5pc of shares.
As recently as Tuesday, the Middle Eastern exchange was stressing its stakebuilding did not constitute a full offer for OMX. However, yesterday it launched a formal bid.
Borse Dubai's chief executive, Per Larsson, who used to be chief executive of OMX, said: " By connecting our platforms and developing a network of exchanges in our target high-growth markets, we will deliver access to greater liquidity and an increasing range of products and services."
He is proposing an enlarged board with representatives from the Nordic region, that would maintain the existing Nordic market model, which encompasses the stock exchanges of seven countries.
OMX noted the offer and said it would consider it. It is understood OMX was taken aback by the move, as Mr Larsson had earlier intimated he was not interested in a bid.
Nasdaq's chief executive, Bob Greifeld, is said to be flying to Stockholm next week to meet Mr Bocker. If Nasdaq lost out on OMX, Mr Greifeld would be in difficulties, having already failed to take over the London Stock Exchange.


text:
Blue Nebula Flight
Updated May 04, 2007 by TheMasterBaron
Comment #1 Friday, May 4, 2007 9:27 AM
Comment #3 Friday, May 4, 2007 3:30 PM
Comment #4 Friday, May 4, 2007 5:18 PM
Comment #5 Friday, May 4, 2007 5:47 PM
BTW, the icon for the Blue Nebula is green also. The file Icon (preview in the OS) is what I mean. Might want to fix that.
Comment #6 Friday, May 4, 2007 8:29 PM
I would love to use MPEG2, but no matter how hard I try, I can't get a reasonable file size. This dream is one minute long, and at 1600x1200. Even after knocking the resolution down to 1440x1080@24fps, it still ended up being 120MB. MPEG2 just doesn't compress all that well.
Comment #7 Saturday, May 5, 2007 12:45 PM
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text:
Europe is a significant region within the video game industry, comprising nearly $20 billion of a $76 billion industry, according to a Big Fish blog post. A key figure of note is that Western Europe has a higher average spend per paying mobile gamer than any other market worldwide - $4.40 average spend versus North America's $3.87 and Asia Pacific's $2.86 (Newzoo). Companies looking to go global often have their games translated into EFIGS – English, French, Italian, German, and Spanish – due to the market reach of these languages and sometimes elect to use Scandinavian languages as well, vastly expanding their global reach to attain a high share of Western European gamers. (Be sure to sign up for our monthly e-newsletter to stay informed of our upcoming pages about the market reach of these languages.)
While it is of course preferable to localize for each individual country, we are aware that is not always an option due to budgetary constraints. That is why we aggregated information on the leading Western European markets to aid you in your localization decisions.
In Western Europe, the UK ranks highest on spending rates for digital game content (MarketResearch.com). Online gaming remains a significant portion of the gaming market in the UK, with 20% of the population playing games online. Mobile gaming is also expected to rise, given that 50% of all tablet owners play games on their tablets.
In addition to the popularity of online and mobile gaming in the UK, it also ranks #2 in the world for console gaming (behind France), with 71% of its nearly 35 million gamers playing games on consoles (Newzoo).
According to Newzoo, France is currently #1 in the world for TV and console gaming, with 72% of nearly 30 million gamers playing on a TV/console.
According to MarketResearch.com, Germany is the leading European country by monthly revenue per paying user, with downloads generating the highest revenue on the online gaming market in 2013. In fact, Newzoo reports that Germany is "#1 in the world when it comes to the payer/player ratio with 70% of gamers paying for games." While console and PC platforms remain popular in Germany, mobile gamers are also increasing the amount of time spent playing, as well as the amount of money spent (PR Newswire). Out of the nearly 40 million gamers in Germany, the highest number of gamers play on social/casual platforms (roughly 32 million), followed by PC/Mac gamers at 26.3 million, smartphone gamers at 23.2 million, and TV/console gamers at 22.7 million.
Numbers for the German market continue to rise, from 38.5 million gamers in 2012 to nearly 40 million in 2014, coupled with the fact that paying players jumped from 64% to 70%, the highest rate of any country in the world (Newzoo). Germany has continued to lead Western European game sales over the years, becoming Europe's largest video game market in 2009, while maintaining strong numbers during the global economic downturn (Wired).
Spain has 19.5 million gamers, with more gamers playing on social and casual platforms (16.6 million), followed by 13.7 million on TV and console, 13.2 million on smartphone, 12.8 million on PC/Mac, and 9.3 million on MMOs.
It is important to localize for Spain's variation of Spanish when attempting to reach this market, as vocabulary, idioms, cultural references, etc. vary greatly between European Spanish and Latin American Spanish. LAI delves into the distinctions between these varieties through a popular Gamasutra article.
Italy has 21 million gamers and is #3 in Europe for tablet gaming, with 25% of Italian gamers playing on tablets (Newzoo).
Europe is certainly one of the most profitable markets for video game consumption in the world, ranking behind Asia Pacific and North America in terms of revenue. Combined with the fact that many of the languages for translation and localization in the area also encompass a significant portion of the global video game market (due to the wide reach of these languages), game companies who typically look to the major languages frequently request to have their games translated to English, French, Italian, German, Spanish, Portuguese, and sometimes Swedish. Be sure to check out our upcoming pages on the market reach of these languages for more information (or subscribe to our monthly e-newletter to stay up-to-date).
LAI strives to keep game developers and publishers updated on key markets for localization. If you find any errors or have additional information to add, please let us know at email@example.com. You can also stay informed of our new webpages by subscribing to LAI's monthly e-newsletter. Please check back soon on LAI's Global Game Industry Statistics page as we frequently update our web content to reflect new industry statistics and market projections. Latest page update: July 2014.


text:
In Memoriam: Chris Toll
More upsetting news: The much-loved Baltimore poet and collage artist Chris Toll has passed away. Ron Silliman featured Toll on his blog a few days ago, including a video by Stephanie Barber of Toll reading at WORMS in Baltimore (also shown below); and HTMLGIANT's Adam Robinson has collected a handful of remembrances from Toll's friends in what New Lights Press founder Aaron Cohick calls on Facebook a "space-collage shrine." The shrine's got words from Melissa Broder, Buck Downs, Heather Christle, Mike Young, Sampson Starkweather, Adam Good, Dorothea Lasky, William Merricle (among others); and R. M. O'Brien, who had this to say:
Chris's importance to me as the model of a visionary poet and as an heretical saint cannot well be explained. I don't think I ever could have made it clear it to the man himself, let alone anyone else now that he's "gone." You either knew him and felt the same, or you knew him and felt your own particular way, or you didn't feel anything cuz you didn't know him.
Chris sent me an email late Tuesday night, the night before the day he "died." I had sent him proofs of his work as it would appear in an anthology I'm editing. To explain why he was sending yet more revisions to a poem and a piece of flash fiction he wrote,
i will explain this as best i can.
i know i'm nobody – i'm a snowflake and i'm drifting toward a bonfire – i know this well – i'm getting hot.
everything we do at every moment is critically important – every deed at every moment in every day should be a living prayer – if we pray hard enough, we will have a New World – and we will have it sooner rather than later.
"I'm a snowflake and I'm drifting toward a bonfire. I'm getting hot." I repeated this to myself as I wander'd around North Baltimore with Asher and my wife Melanie. It was a sustaining mantra, and a last gift from Chris. I think he knew I was sensitive and prone to emotional meltdowns and that poetry was stronger for me than religion in a crisis.
When people I love die, I worry about their last conscious thought. Was it a peaceful one? Was it fill'd with hangups, terror? Mercifully, Chris answered that anxiety: He was nobody. He was a snowflake. He melted in a bonfire.
A great loss for poetry. You can read more about and by Chris here, here, and here. Photo originally published at BOMB.


text:
She is the mystery in the middle of the California governor's race.
Three days ago, Republican Meg Whitman's former housekeeper accused her of knowing for years she was an illegal immigrant but kept her on the payroll anyway - an allegation that upended the campaign and left Whitman struggling to steady her candidacy just weeks before election day.
Nicky Diaz Santillan, a 39-year-old mother of three, hasn't spoken a word in public since and left a trail of questions about her story and how she ended up as the client of a high-powered Los Angeles lawyer with longtime Democratic ties, Gloria Allred.
Under Allred's guidance, Diaz Santillan hasn't answered a single question from reporters since that day. No one answered the door Wednesday at an address listed for Diaz Santillan in a well-kept middle-class neighborhood in Union City, a San Francisco suburb.
A phone number listed for the family has been disconnected.
Allred has said little about Diaz Santillan's whereabouts or thinking from the time she was fired by Whitman in June 2009 until she appeared at Allred's side at her Los Angeles law office. Allred says the case was referred to her by another lawyer, but will not reveal that person's name.
"Nicky spent a great deal of time deliberating as to whether or not she could, would or should do or say anything," Allred told reporters. "Finally ... she decided, yes, she should do something. ... She decided to talk to an attorney."
Whitman has accused her Democratic opponent, Jerry Brown, of orchestrating a "smear attack" on her candidacy. Allred says she has no connection to Brown's campaign, though she has donated money to him in the past.
Whitman says Diaz Santillan provided a valid but fraudulently obtained Social Security card and driver's license when she was hired through an employment agency in 2000, and denies she knew about her illegal status until told by Diaz Santillan in June 2009.
Whitman promptly fired her.
The rough outlines of Diaz Santillan's life were laid out in her 2000 employment application. She said she went to high school and college in Mexico City and would like to go back to school to study computer administration.
She said she has 11 brothers and sisters, eight of them living in the San Francisco Bay area. Whitman's campaign says Diaz Santillan used her sister's documents in her fraudulent application.
In her statement, Diaz Santillan said she pleaded with Whitman to get her an immigration attorney but was spurned and fired from the $23-an-hour position she held for nine years.
"I was shocked," she said.


text:
The Richmond County Georgia Forestry Commission will move its Tobacco Road office to a smaller building by next month.
Officials say the move to an office off the beaten path inside the Spirit Creek Educational Forest in Hephzibah will save money and should have only a minimal effect on response times.
"Yes, it could slow us down somewhat, but we don't really expect very much change in how we operate," said Steve Abbott, the chief senior ranger for the commission's Richmond County division, which also covers Columbia County.
Lately, though, that operation has been busy, with forestry rangers responding to more wildfires as a result of dry conditions.
"There are more fires this year due to dry and drought conditions, and also due to incendiary arson incidents," Mr. Abbott said.
Since the Georgia Forestry's 2009 fiscal year started in July, the local forestry office has responded to 25 wildfires in Richmond County. In the 2008 fiscal year, the office responded to 41 wildfires there.
By Nov. 3, Mr. Abbott and his staff will have moved from their 2615 Tobacco Road office to the existing facility at the educational forest.
Mr. Abbott couldn't provide figures on how much savings will occur with the move, but he said it will be "significant."
"It makes economic sense to consolidate to the new office," he said of the building, which was formerly a fire station and is at least 30 years old.
Mr. Abbott said the Tobacco Road forestry office employs two rangers who manage wildfires that typically occur "when people burn leaves and those fires become uncontrolled."
"Human error is the No. 1 cause of these fires," he said.
Since Oct. 1, the commission has issued more than 800 burn permits for Richmond and Columbia counties. Outdoor burning season runs through April 30.
Reach Timothy Cox at (706) 823-3217 or email@example.com.
- Fire control and protecting the natural resources of Georgia
- Managing timber through controlled burns
- Effectively using bulldozers and other heavy equipment to control woods fires.
Fiscal year 2008 -- 41 wildfires in Richmond County
Fiscal year 2008 -- 36 wildfires in Columbia County
July 1 to Oct. 16 -- Rangers fought 25 wildfires in Richmond County
July 1 to Oct. 16 -- Rangers fought 7 wildfires in Columbia County
Fiscal Year - Columbia County - Richmond County
2008 - 36 - 41
2009* - 7 - 25
* July 1 to Oct. 16
Source: Georgia Forestry Commission


text:
Raekwon – "Flawless" [LISTEN]
Thursdays belong to Raekwon if old school grooves are your thing. For his seventh #TBT release, the veteran wordsmith shines on a track titled "Flawless."
Listeners will be confused at first, because the sounds of Willie Hutch's "I Choose You" from The Mack soundtrack, but the soundscape quickly gets smoother. The Chef throws lyrical darts over Luther Vandross' 1988 fan-favorite "For You To Love." Those familiar with the record know that it's as smooth as Raekwon's vocals.
A hilarious clip from Antonio Fargas' "Fly Guy" character from I'm Gonna Git You Sucka makes the cypher complete.
Stream Raekwon's "Flawless" below.
Photo: Instagram


text:
Well, with all the stories I have written in the last week or so on the draft, believe it or not, in reviewing some of my notes, I actually found some comments from scouting director Joe Jordan that I have not yet published.
So let's clean out this quote book once and for all.
I asked Jordan if he expects to sign players to over-slot contracts as the O's did with a few picks in the 2009 draft?
"I expect to have the ability to do whatever we feel like we need to do. There is a budget, there always is. But we've done a good job of spreading the risk out and this year won't be any different. These guys have always given me everything I've asked for, basically."
The Orioles spent 8.7 million total on draft picks last year and I asked if they would spend more this year.
"I don't know. I expect to spend a lot more, but who knows if I will," Jordan said with a laugh. "We'll have a full budget like we always do.
"I didn't envision at this time last year (a few days before the draft), doing everything that we did (in 2009). Those answers come in the final days of your meetings. What guy will fall because of money and are we ready? We'll get to that and try to identify some of those guys and do it again."
Heading into the draft Jordan didn't see any more risk whether he took a college or high school player with the third pick.
"Usually with players taken this highly, there is a pretty good success rate. There are examples on the other side of it, high school or college. I'm not hung up one way or the other.
"I like taking college players. You know if I had Matt Wieters there or Matusz, I would feel great about that."
Jordan keeps team president Andy MacPhail advised of what he and his staff plan and do leading up to the draft, but Jordan is the one in the end making the draft picks.
"It will be my decision. But I recognize that Andy has been in the business for a long time and worked with a lot of scouting directors. He has a great insight for me and a different perspective as I lay things out for him.
"It's my decision, but I get input from others in our organization. John Stockstill has done my job. John and I have talked a few times and he's been very good about stepping back and giving me an objective opinion.
"Yeah, I'll make the call but with input from a lot of different people, mainly my staff. But there are some very good resources in our organization and I'm not too big to draw on any of them."
I also asked Jordan to rate this draft overall.
"I think it's a good draft, not a great draft. I'm glad we are picking high. I like the options there vs. maybe if we're in the middle or toward the end of the round.
"There are a lot of arms. In most people's minds, it's probably not as heavy on college position players and left-handers are little light in sheer numbers. But it's a good draft, we'll see."
The Orioles first pick today will be the third selection in the third round, the 85th pick overall. Jordan has said he would prefer a college hitter with that selection unless a player the Orioles had rated high on their draft board falls and is available with that pick.
The Orioles fourth-round pick will be the 118th overall selection and they will have every 30th pick after that.
Today the draft resumes at Noon with clubs making picks for rounds two through 30. Wednesday the clubs conclude the draft with rounds 31 through 50.


text:
The company was carrying out an assessment of all ongoing projects across the world so that it can work efficiently in this phase of economic slowdown and give returns to their investors.
While the underworld money trail has often lead to do the door steps of some of the biggest Bollywood producers, the focus this time is on the actors who are earning in crores with each film.
Telecom operators have installed 48,000 towers in the last 45 days, out of 60,000 towers they promised to install in 100 days at a meeting held in June.
Defending the slow-paced growth of AirAsia India, group chief Tony Fernandes said the aviation sector here was a "double marathon" and not a "sprint".
Air India will drop fares on four key routes--Delhi-Mumbai, Delhi-Chennai, Delhi-Kolkata and Delhi-Bengaluru--four hours before the departure of flights to these destinations.
In the US Fed, the Chairman and Vice-Chairman serve terms of four years, and may be reappointed to those roles who in turn serve until their terms as Governors expire.
Ravinder S Aurora, Group Head, Senior vice president, Global Policy Affairs and Community Relations, MasterCard, said the global time payment processing firm in association with the Confederation of All India Traders has trained over 50,000 traders across the country under the digital campaign exercise.
Reserve Bank of India Governor Raghuram Rajan believes a good monsoon and supply management will act as a counter to inflationary pressures.
The Central Drugs Standard Control Organisation (CDSCO) discovered that some batches of Combiflam tablets had delayed disintegration time which means time taken for breakdown of a tablet in the human body was unnecessarily high.
The Serious Fraud Investigation Office is looking into whether the valuation was deliberately inflated to get more funds from banks and siphon off money for purposes other than proposed investment in the airline.
Home buyers can now look forward to a better deal from builders with the Real Estate (Regulation and Development) Bill, 2013, being approved by the Lok Sabha on Tuesday five days after it was cleared by the Rajya Sabha.
Public sector oil marketing companies on Wednesday announced a cut in retail selling price of petrol by 32 paise a litre and increased diesel prices by 28 paise a litre in Delhi.
A benchmark index of Indian equities markets, the 30-scrip Sensitive Index (Sensex), on Wednesday was trading 141.51 points, or 0.59 per cent, down during the morning session.
Growth in the industrial sector has turned out to be lower while the farm and services sector growth rates have ended up higher than earlier estimates.
The bank saw its gross non-performing assets (NPA) grow nearly three-fold to Rs 6,544 crore during the the third quarter that also pushed total provisions to Rs 2,844 crore from Rs 980 crore a year ago.
The telecom regulator says 700 MHz band should go under the hammer for base price of Rs 11,485 crore and auction of 800 MHz band, widely in demand for 4G services, at a base price of Rs 5,829 per MHz.
Mukesh Ambani-run Reliance Industries holds the distinction of building the biggest refinery in India till now.
This is the 14th straight month since November 2014 when the wholesale inflation has remained in the negative zone.
Madhya Pradesh Tourist Development Corporation has constructed a boat club and restaurant at Hanuwantiya with an investment of Rs 8 crore. Plantation has been done to ensure greenery at the island besides water sports complex is also being set up, he said.
Major losers that dragged down the Sensex and Nifty were Tata Motors, Bharti Airtel, Adani Ports, HDFC Ltgd, BHEL, Lupin, ICICI Bank, SBI, RIL, Sun Pharma,Axis Bank, GAIL, Cipla, Hero MotoCorp, L&T, Coal India, M&M, Infosys and TCS.


text:
Bank of England expected to keep interest rates on hold at 0.5%
The Bank of England is expected to keep interest rates on hold today amid mounting concern over a slowdown in the economy.
Rates have remained unchanged at 0.5% for more than six years and are now not expected to rise until 2016 after reports signalled easing growth in the UK and global economy.
The Bank's Monetary Policy Committee (MPC) is likely to weigh up developments such as accelerating wage growth and the country's recovering economy, against the global turmoil caused by China's slowing trade performance and the UK's sluggish export growth.
Most economists forecast the MPC will vote eight to one in favour of keeping rates unchanged, mirroring last month's vote.
It is expected that only MPC member Ian McCafferty will continue to dissent on the ''no change'' position, although policymakers Martin Weale and Kristin Forbes have both indicated that interest rates will need to rise sooner rather than later.
Economists said disappointing global manufacturing data in recent days will ease the pressure on MPC members to lift interest rates, while forecasts suggest UK growth in the third quarter eased back, to 0.6% or even 0.5% from 0.7% in the previous three months.
In the UK, employment in the manufacturing sector fell for the first time in two-and-a-half years at the end of a ''lacklustre'' September, according to the closely-watched CIPS/Markit purchasing managers' index (PMI) survey.
The report added September rounded off one of the weakest quarters during the past two years, which saw factory job losses registered for the first time since April 2013.
It blamed the strong pound and weak export orders for the slowdown.
This report came amid a raft of weak manufacturing data from China, the US and the eurozone.
Expectations for a rise in US interest rates has been put back after job growth in the US, the world's powerhouse economy, slowed in September, and job gains for July and August were lower than previously thought, a sour note for a labour market that had been steadily improving.
The US added 142,000 jobs last month, although the economy has put on an average of 198,000 new jobs a month this year.
There was further gloom on the global picture yesterday when the International Monetary Fund (IMF) cut its growth forecasts to their lowest level in six years, predicting world growth of 3.1% this year, from its previous projection of 3.3%.
The Washington-based fund said a combination of Chinese slowdown, sliding commodity prices and uncertainty over when the US hikes interest rates would lead the world to its lowest annual growth rate since 2009.
But the IMF increased its forecast for UK growth this year by 0.1% to 2.5% from July, and next year it kept its expectation of 2.2% growth unchanged.
Howard Archer, chief UK and European economist at IHS Global Insight, said: ''There can be little - if any - doubt that the Bank of England will keep interest rates unchanged at 0.5% at the conclusion of the October MPC meeting on Thursday.''
Mr Archer added that it is ''currently an extremely tight call'' as to whether the Bank of England lifts interest rates from 0.5% to 0.75% around February, or holds fire until nearer mid-2016.
The MPC is also expected to vote nine to zero in favour of keeping the UK's quantitative easing total at £375 billion.


text:
Boys soccer: Irish blanked in final two games
The final two games of the regular season played out in similar fashion for the Rosemount boys soccer team.
The Irish managed to hang within a goal against a ranked opponent before a couple of late scores resulted in a pair of 3-0 losses. The first setback was against top-ranked (Class 2A) Eastview last Tuesday at Irish Stadium and the second against No. 8 Eagan on the road last Thursday. It was the ninth time the team has been shut out in 15 games this season.
The homecoming game against No. 1 Eastview, the final home game for the team's seven seniors, was especially memorable for head coach Mike Floersch.
"The players played great and worked hard," he said. "Their effort was outstanding. We held Eastview to only one goal until the last 10 minutes when they scored two. It was a great night with a ton of fans."
Rosemount finished the regular season 3-10-2 and earned the No. 7 seed in Section 3AA. That earned them a first-round playoff game against No. 2 Eagan on Tuesday.


text:
This product is no longer available.
You can try these similar gifts instead.
Sterling Silver Football Cuff Links
He might rather be at the game, or he might wish that he was on the field making a long pass to his teammate. But when he has to dress up, he'll show his love for the sport by wearing these handsome cufflinks.


text:
JcrOffroad Protyping: Crusader Roof Rack! Revisted!
Many of you might remember our attempt at prototyping a new roof rack. We built it out of all flat and the prototype was WAY to heavy and the idea just wasn't coming together.
This was our the design we failed at making into a viable product:
So we finally decided to hit the drawing board again!
Our #1 issue was to be able to make it modular to allow for being broken down for shipping. Our last Low profile rack would cost us $175 for UPS ground :icon_sad:
After some brain storming, we came up with a nice hybrid idea between our old tube design and our new flat steel idea:
Possible options:
No Lightbar
Led Lightbar
Halogen Lightbar
Adjustable TireMount
Hi-Lift Mount
Half Sides (for front or rear section)
Full Sides
Middle Extension (for full length)
Mounts for different vehicles (TJ/YJ/CJ/LJ/JK/ZJ/KJ/ect)
Turn into metal:
The hoop is a bolt on deal, the rack bolts together in the middle.
These are some optional sides we are kicking around:
2 Attachment(s)
looks way to tall IMO. id really like to see the light bar mount similar to a visor, like a mix between the rigid mounts for JKs and what heavymetal runs with his cage
Personally, I like it. Any ideas on cost?
What did you do with the first prototype? Want to sell it?
Just a small update.
Q: Light bar option?
A: We have plans to make something available but at this time nothing is in development.
Q: Why not full length?
A: Shipping; and this is the same size as our previous low profile utility rack. We plan to also offer an extension for those who would like to go full length, but again nothing has being designed.
Q: Is that too tall?
A: As you can see a spare tire still sits higher than the light bar its self, and the clearance with the lights that are mounted on there is about 3/4" if you move the back closer to the tailgate you lose the slope of the roofline and fall all the way down to about 1/4"-3/8" of clearance.
Q: Highlift mount?
A: Unfortunately this picture didn't capture it however there is an optional highligt mount on the opposite side.
Q: Can I see the tire mount?
A: The tire mount uses a similar mounting and adjustable as our rear bumper tire carriers so you can keep it as close or as far away as possible.
Q: Rotopax?
A: We have kicked around a couple ideas and we should easily be able to make a mount for 2-4 cans easily.
Q: Price and Availability?
A: At this time we don't have a ball park for the pricing, as this rack is modular it will vary greatly in price. You will be able to start with the base rack (a front and back) and build it to however you want.
I'm absolutely interested in one just like that, perfect for pre-runner style XJs. Even if this doesn't go to production I'd harass you guys for that one specifically.
Looks like if the front half was offered separately it would fit on MJ roofs too.
Made some more progress. Tire mounted, put some bigger lights on it!
Me likey!
looks nice but i wouldnt run it. its to tall. That thing is going to get caught on everything on the trail.
How much does it weigh?
how much does it weigh? and can I get it without the light bar or sides?
And how about some sort of system so tie downs can actually grab and have something edge to edge on the rack?
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