A copolyester of the reaction product of: (a) one or more aromatic dicarboxylic acids or an ester thereof; (b) one or more aliphatic dicarboxylic acids or an ester thereof; and (c) isosorbide. The polyesters are useful to form articles of increased biodegradability.

This invention relates to copolyesters that can exhibit an improved rate of biodegradation more amenable to solid waste disposal. The invention also relates to methods of making and using the copolyesters.
The inadequate treatment of municipal solid waste deposited in landfills and the increasing addition of nondegradable materials, including plastics, to municipal solid waste streams are combining to drastically reduce the number of landfills available and to increase the costs of municipal solid waste disposal. While recycling of reusable components of the solid waste is desirable in many instances, the costs of recycling and the infrastructure required to recycle materials is sometimes prohibitive. In addition, there are some products, which do not easily fit into the framework of recycling. One alternative approach is the composting of non-recyclable solid waste a recognized and growing method to reduce solid waste volume for landfilling. Products from the composted waste can be used to improve the fertility of fields and gardens. However, one of the limitations to marketing such composted product is the visible contamination by undegraded plastic, such as film or fiber fragments.
Polymer components are sought that are useful in disposable products and which are degraded into less contaminating forms under the conditions typically existing in waste composting processes. It is further desirable to provide disposable components, which will not only degrade aerobically/anaerobically in composting, but will continue to degrade in the soil or landfill.
Polyesters have been considered for biodegradable articles and end-uses in the past. These biodegradable polyesters can be characterized as belonging to three general classes; aliphatic polyesters (polyesters derived solely from aliphatic dicarboxylic acids), aliphatic-aromatic polyesters (polyesters derived from a mixture of aliphatic dicarboxylic acids and aromatic dicarboxylic acids), and sulfonated polyesters derived from a mixture of aliphatic dicarboxylic acids and aromatic dicarboxylic acids and, in addition, incorporating a sulfonated monomer, such as the salts of 5-sulfoisophthalic acid.
A shortcoming of the above mentioned polyesters is that they often do not provide a composition which combines both high temperature characteristics, which are required by many enduses, such as dual ovenable food trays and the like, with a high rate of biodegradation, as desired to avoid the filling of landfills. It has been generally found that the biodegradation rate of the polyester may be enhanced through the addition of greater amounts of aliphatic dicarboxylic acids. At the same time, it has been generally found that the incorporation of such aliphatic dicarboxylic acids into a polyester composition tends to degrade the thermal properties of the polyester composition, as measured through the glass transition temperature, (Tg).
Isosorbide has been incorporated as a monomer into aliphatic and aromatic polyesters. A recent review is found in Hans R. Kricheldorf, et. al., J. M. S.-Rev. Macromol. Chem. Phys., C37(4), pp. 599-631 (1997). However it is generally believed that secondary alcohols such as isosorbide have poor reactivity and are sensitive to acid-catalyzed reactions.
One skilled in the art was thus confronted by three distinct art areas; (i) the aliphatic-aromatic polyesters, which suffered from relatively low thermal properties, such as glass transition temperatures; (ii) the aliphatic isosorbide polyester art, which suffered from low molecular weights and thermal properties; and (iii) the aromatic isosorbide polyester art, which suffered from a low biodegradation rate.
The present inventor has surprisingly found that the aliphatic-aromatic isosorbide copolyesters of the present invention combine good molecular weight and thermal properties with improved biodegradability.
The present invention provides a copolyester comprising the polymerization product of:
(a) one or more aromatic dicarboxylic acids or an ester thereof;
(b) one or more aliphatic dicarboxylic acids or an ester thereof, and
(c) isosorbide.
The aliphatic-aromatic copolyesters which incorporate isosorbide of the present invention are found to often avoid many of the shortcomings found in the art. The polymers of the invention can provide a combination of a higher biodegradation rate with higher thermal properties than found in the art.
Further objects, features and advantages of the invention will become apparent form the detailed description that follows.
The copolyesters of the present invention include isosorbide, which is the diol 1,4:3,6-dianhydro-D-sorbitol. Isosorbide is readily made from renewable resources, such as sugars and starches. For example, isosorbide can be made from D-glucose by hydrogenation followed by acid-catalyzed dehydration. The preparation of isosorbide is known within the literature in, for example, G. Fleche, et. al., Starch/Starke, 38(1), pp. 26-30 (1986).
The terms glycol, diol and dihydric alcohol as used herein refer to similar general compositions of a primary, secondary or tertiary alcohol containing two hydroxyl groups and can be used interchangeably. The term glycol is more often used in the art to characterize low molecular weight alcohols such as ethylene glycol and propylene glycol. Diol and dihydric alcohol are typically applied to higher molecular weight alcohols, including polymeric diols.
Any aromatic dicarboxylic acid known in the art can be used. Useful aromatic dicarboxylic acids include unsubstituted and substituted aromatic dicarboxylic acids and the lower alkyl (C1-C6) esters of aromatic dicarboxylic acids; e.g., having from 8 carbons to 20 carbons. Examples of useful diacid moieties include those derived from terephthalates, isophthalates, naphthalates, and bibenzoates. Specific examples of useful aromatic dicarboxylic acid components include terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, 2,6-napthalene dicarboxylic acid, dimethyl-2,6-naphthalate, 2,7-naphthalenedicarboxylic acid, dimethyl-2,7-naphthalate, 3,4xe2x80x2-diphenyl ether dicarboxylic acid, dimethyl-3,4xe2x80x2diphenyl ether dicarboxylate, 4,4xe2x80x2-diphenyl ether dicarboxylic acid, dimethyl-4,4xe2x80x2-diphenyl ether dicarboxylate, 3,4xe2x80x2-diphenyl sulfide dicarboxylic acid, dimethyl-3,4xe2x80x2-diphenyl sulfide dicarboxylate, 4,4xe2x80x2-diphenyl sulfide dicarboxylic acid, dimethyl-4,4xe2x80x2-diphenyl sulfide dicarboxylate, 3,4xe2x80x2-diphenyl sulfone dicarboxylic acid, dimethyl-3,4xe2x80x2-diphenyl sulfone dicarboxylate, 4,4xe2x80x2-diphenyl sulfone dicarboxylic acid, dimethyl-4,4xe2x80x2-diphenyl sulfone dicarboxylate, 3,4xe2x80x2-benzophenonedicarboxylic acid, dimethyl-3,4xe2x80x2-benzophenonedicarboxylate, 4,4xe2x80x2-benzophenonedicarboxylic acid, dimethyl-4,4xe2x80x2-benzophenonedicarboxylate, 1,4-naphthalene dicarboxylic acid, dimethyl-1,4-naphthalate, 4,4xe2x80x2-methylene bis(benzoic acid), dimethyl-4,4xe2x80x2-methylenebis(benzoate), and the like and mixtures of two or more thereof. Preferably, the aromatic dicarboxylic acid component is derived from terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, 2,6-naphthalene dicarboxylic acid, dimethyl-2,6-naphthalate, or mixtures of two or more thereof.
Any aliphatic dicarboxylic acid known in the art can be used within the present invention. Useful aliphatic dicarboxylic acid components include unsubstituted (C1-C6), or substituted; linear, branched, or cyclic aliphatic dicarboxylic acids, and the lower alkyl esters thereof, preferably having 2-36 carbon atoms. Examples of useful aliphatic dicarboxylic acid components include, oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, succinic acid, dimethyl succinate, methylsuccinc acid, glutaric acid, dimethyl glutarate, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, dimethyl adipate, 3-methyladipic acid, 2,2,5,5-tetramethylhexanedioic acid, pimelic acid, suberic acid, azelaic acid, dimethyl azelate, sebacic acid, 1,11-undecanedicarboxylic acid, 1,10-decanedicarboxylic acid, undecanedioic acid, 1,12-dodecanedicarboxylic acid, hexadecanedioic acid, docosanedioic acid, tetracosanedioic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, dimethyl-1,4-cyclohexanedicarboxylate, 1,3-cyclohexanedicarboxylic acid, dimethyl-1,3-cyclohexanedicarboxylate, 1,1-cyclohexanediacetic acid, and the like and mixtures of two or more thereof. Preferred aliphatic acids or esters include succinic acid, dimethyl succinate, glutaric acid, dimethyl glutarate, adipic acid, dimethyl adipate, and dimer acid.
The polyester can be formed with an optional glycol. Any glycol known in the art can be used as the optional dihydric alcohol of the invention. Examples include unsubstituted or substituted; straight chain, branched, cyclic aliphatic, aliphatic-aromatic, or aromatic diols having e.g., from 2 carbon atoms to 36 carbon atoms and poly(alkylene ether) glycols with molecular weights preferably between about 250 to about 4,000. Specific examples of the useful glycol component include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, dimer diol, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1 .0/2.6]decane, 1,4-cyclohexanedimethanol, di(ethylene glycol), tri(ethylene glycol), poly(ethylene ether) glycols, poly(butylene ether) glycols and the like and mixtures of two or more. Preferred dihydric alcohols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and poly(ethylene ether) glycols.
The polymer may be formed from an optional polyfunctional branching agent, such as any material with three or more carboxylic acid functions, hydroxy functions or a mixture thereof Specific examples of useful polyfunctional branching agent component include 1,2,4-benzenetricarboxylic acid (trimellitic acid), trimethyl-1,2,4-benzenetricarboxylate, 1,2,4-benzenetricarboxylic anhydride (trimellitic anhydride), 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), 1,2,4,5-benzenetetracarboxylic dianhydride (pyromellitic anhydride), 3,3xe2x80x2,4,4xe2x80x2-benzophenonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, citric acid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, pentaerythritol, 2-(hydroxymethyl)-1,3-propanediol, 2,2-bis(hydroxymethyl)propionic acid, and the like and mixtures of two or more thereof. The polyfunctional branching agent may be included when higher resin melt viscosity is desired for specific enduses. Examples of such end-uses include melt extrusion coatings, melt blown films or containers, foam and the like.
To give the desired physical properties, the aliphatic-aromatic copolyesters which incorporate isosorbide of the present invention should preferably have an inherent viscosity, which is an indicator of molecular weight, of least equal to or greater than about 0.15. More desirably, the inherent viscosity, (IV), of the aliphatic-aromatic copolyesters which include isosorbide will be equal to or greater than about 0.35 dL/g. IV is measured on a 0.5 percent (weight/volume) solution of the copolyester in a 50:50 (weight) solution of a trifluoroacetic acid:dichloromethane solvent system at room temperature. Even higher inherent viscosity""s are desirable for many other applications, such as films, bottles, sheet, molding resin, and the like. The polymerization conditions may be adjusted to obtain the desired inherent viscosity""s up to at least about 0.5 and desirably higher than 0.65 dL/g. Further processing of the copolyester may achieve inherent viscosity""s of 0.7, 0.8, 0.9, 1.0, 1.5, 2.0 dL/g and even higher.
The polyesters of the present invention can be prepared by conventional polycondensation techniques. The product compositions may vary somewhat based on the method of preparation used, particularly in the amount of diol that is present within the polymer. These methods include the reaction of the diol monomers with the acid chlorides. For example, acid chlorides of the aromatic dicarboxylic acid component and the aliphatic dicarboxylic acid component may be combined with the isosorbide and the other glycol component in a solvent, such as toluene, in the presence of a base, such as pyridine, which neutralizes the hydrochloric acid as it is produced. Such procedures are known. See, for example, R. Storbeck, et. al., J. Appl. Polymer Science, Vol. 59, pp. 1199-1202 (1996).
Other well known variations using acid chlorides may also be used, such as an interfacial polymerization method, or the monomers may simply be stirred together while heating.
When the polymer is made using acid chlorides, the ratio of the monomer units in the product polymer is about the same as the ratio of reacting monomers. Therefore, the ratio of monomers charged to the reactor is about the same as the desired ratio in the product. An approximately stoichiometric equivalent of the diol components and the diacid components can be used to obtain a higher molecular weight polymer.
Preferably, the copolyesters are produced through a melt polymerization method. In the melt polymerization method, the aromatic dicarboxylic acid component, (either as acids, esters, or mixtures thereof), the aliphatic dicarboxylic acid component, (either as acids, esters, or mixtures thereof), the isosorbide, the other optional glycol component and optionally the polyfunctional branching agent, are combined in the presence of a catalyst at a temperature high enough such that the monomers combine to form esters and diesters, then oligomers, and finally polymers. The polymeric product at the end of the polymerization process is a molten product. Generally, the diol component and the isosorbide are volatile and distill from the reactor as the polymerization proceeds. Such procedures are known. See, for example, Charbonneau, et. al., in U.S. Pat. No. 6,063,464 and the references cited therein.
The melt process conditions of the present invention, particularly the amounts of monomers used, depend on the polymer composition that is desired. The amount of isosorbide, the other glycol or dihydric alcohol component, aromatic dicarboxylic acid component, aliphatic acid component, and branching agent are desirably chosen so that the final polymeric product contains the desired amounts of the various monomer units, desirably with approximately equimolar amounts of monomer units derived from the respective diol and diacid components. Because of the volatility of some of the monomers, especially some of the glycol components and isosorbide, and depending on such variables as whether the reactor is sealed, (i.e.; is under pressure), the polymerization temperature ramp rate, and the efficiency of the distillation columns used in synthesizing the polymer, some of the monomers may need to be included in excess at the beginning of the polymerization reaction and removed by distillation as the reaction proceeds. This is particularly true of the glycol component and of isosorbide.
The amount of monomers to be charged to a particular reactor is readily determined by a skilled practitioner, but often will be in the ranges below. Excesses of the diacid, diol, and isosorbide are often desirably charged, and the excess diacid, diol and isosorbide is desirably removed by distillation or other means of evaporation as the polymerization reaction proceeds. Isosorbide is desirably charged at a level 20 to 100 percent greater than the desired incorporation level in the final polymer. The other optional glycol component is desirably charged at a level 0 to 100 percent greater than the desired incorporation level in the final product. For examples of the other glycol component which are volatile under the polymerization conditions, such as ethylene glycol, 1,3-propanediol, or 1,4-butanediol, 30 to 100 percent excesses are desirably charged. For less volatile examples of the other glycol component, such as dimer diol, no excesses need be desirably charged. Typically the diacid component is not added in excess because they are typically less volatile. However, if the acids are volatile, it may be desired to add the acids in excess.
The ranges given below for the monomers vary because of the wide variation in the monomer loss during polymerization, depending on the efficiency of distillation columns and other kinds of recovery and recycle systems and the like. Exact amounts of monomers that are charged to a specific reactor to achieve a specific composition are readily determined by a skilled practitioner.
While the copolyesters can include any amount of the monomer, generally about 98 to about 20 mole percent, preferably about 90 to about 40 mole percent, more preferably about 80 to about 50 mole percent of aromatic dicarboxylic acid (based on total dicarboxylic acids); about 2 to about 80 mole percent, preferably about 10 to about 60 mole percent, more preferably about 20 to about 50 mole percent of aliphatic dicarboxylic acid (based on total dicarboxylic acids); about 100 to about 1 mole percent, preferably about 50 to about 2 mole percent, more preferably about 25 to about 5 mole percent of isosorbide (based on total glycols (diols)); and 0 to about 99 mole percent, preferably about 50 to about 98 mole percent, more preferably about 75 to about 95 mole percent of other glycol (based on total glycols (diols)); 0 to about 5 mole percent, preferably 0.5 to about 2.5 mole percent, more preferably about 1 to about 1.0 mole percent of polyfunctional branching agent (based on total glycols or total dicarboxylic acids, depending on the chemical functionality of the used polyfunctional branching agent); are used.
These ranges are for monomers incorporated into the polymer. For the reasons discussed above, the amount of monomer required to achieve the incorporation level desired will vary widely based on the nature of monomer chosen. This disparity between added monomer and monomer level incorporated is further demonstrated within the examples. For example, the incorporation rate of isosorbide can be at 50%, and other glycols, such as ethylene glycol, is typically added in 30 to 100 percent excesses.
In the polymerization process, the monomers are combined, and are heated generally with mixing with a catalyst or catalyst mixture to a temperature, generally in the range of 230xc2x0 C. to about 300xc2x0 C., desirably 250xc2x0 C. to 295xc2x0 C. The exact conditions and the catalysts depend, for example, on whether the diacids are polymerized as true acids or as dimethyl esters. The catalyst may be included initially with the reactants, and/or may be added one or more times to the mixture as it is heated. The catalyst used may be modified as the reaction proceeds. The heating and stirring are continued for a sufficient time and to a sufficient temperature, generally with removal by distillation of excess reactants, to yield a molten polymer having a high enough molecular weight to be suitable for making fabricated products.
Any desired catalyst may be used. Catalysts that may be used include salts of Li, Ca, Mg, Mn, Zn, Pb, Sb, Sn, Ge, and Ti, such as acetate salts and oxides, including glycol adducts, and Ti alkoxides. These are generally known in the art, and the specific catalyst or combination or sequence of catalysts used may be readily selected by a skilled practitioner. The preferred catalyst and preferred conditions differ depending on, for example, whether the diacid monomer is polymerized as the free diacid or as a dimethyl ester and the chemical identity of the other optional glycol component.
The monomer composition of the polymer is chosen for specific uses and for specific sets of properties. For uses where a partially crystalline polymer is desired, as for example food and beverage containers, such as hot fill or cold fill bottles, fibers, and films, the polymer will generally have a monomer composition in the range of about 1.0 to 10.0 mole percent, preferably about 1 to about 5 mole percent of isosorbide moieties, based on total glycol.
For applications where it is desirable to have an amorphous polymer, such as would be the case to make transparent optical articles or solvent soluble copolyesters, the amount of isosorbide moiety is generally greater than about 2.0 mole percent, again based on total glycol.
Polymers can be made by the melt condensation process described above having adequate inherent viscosity for many applications. Solid state polymerization may be used to achieve even higher inherent viscosity""s (molecular weights).
The product made by melt polymerization, after extruding, cooling and pelletizing, may be essentially noncrystalline. Noncrystalline material can be made semicrystalline by heating it to a temperature above the glass transition temperature for an extended period of time. This induces crystallization so that the product can then be heated to a higher temperature to raise the molecular weight.
The polymer may also be crystallized prior to solid state polymerization by treatment with a relatively poor solvent for polyesters which induces crystallization. Such solvents reduce the glass transition temperature (Tg) allowing for crystallization. Solvent induced crystallization is known for polyesters and is described in U.S. Pat. Nos. 5,164,478 and 3,684,766.
The semicrystalline polymer can be subjected to solid state polymerization by placing the pelletized or pulverized polymer into a stream of an inert gas, usually nitrogen, or under a vacuum of about 1 Torr, at an elevated temperature, but below the melting temperature of the polymer for an extended period of time.
The present copolyesters are generally substantially biodegradable compared to other copolyesters known in the art. For example, when compared with comparable aromatic isosorbide polyesters known within the art which do not incorporate an aliphatic dicarboxylic acid component, the aliphatic-aromatic copolyesters which incorporate isosorbide of the present invention can have a biodegradation rate at least twice that found for the comparable aromatic isosorbide polyesters of the art, as can be measured by the below mentioned ISO 14855 composting method. Also, the aliphatic-aromatic copolyesters which incorporate isosorbide of the present invention often have greater thermal properties, as can be measured by the glass transition temperature, (Tg), crystalline melting point, (T m), or heat deflection temperature, (HDT), of articles produced from the copolyesters of the present invention, than found for the corresponding aliphatic isosorbide polyesters and the aliphatic-aromatic copolyesters of the art.
Some of the above described aliphatic-aromatic copolyesters which incorporate isosorbide have both biodegradable and solvent solubility in common, non-halogenated, polar solvents. Examples of the non-halogenated, polar solvents include tetrahydrofuran, dimethyl acetamide, dimethyl formamide, N-methylpyrollidone, dimethylsulfoxide, and the like. Some of the aliphatic-aromatic copolyesters which incorporate isosorbide of the current invention are readily soluble in said solvents and the resulting polymer solutions provide clear films.
The copolyesters of the present invention may be used with additives known within the art. Such additives may include thermal stabilizers, for example, phenolic antioxidants, secondary thermal stabilizers, for example, thioethers and phosphites, UV absorbers, for example benzophenone- and benzotriazole-derivatives, UV stabilizers, for example, hindered amine light stabilizers (HALS), and the like. The additives may further include plasticizers, processing aides, flow enhancing additives, lubricants, pigments, flame retardants, impact modifiers, nucleating agents to increase crystallinity, antiblocking agents such as silica and the like. In addition, the compositions of the present invention may be filled with, for example, wood flour, gypsum, wollastonite, chalk, kaolin, clay, silicon oxide, calcium terephthalate, aluminum oxide, titanium oxide, calcium phosphate, lithium fluoride, cellulose, starch, chemically modified starch, thermoplastic starch, calcium carbonate, reinforcing agents, such as glass, and the like. The compositions of the present invention may also find use as a component of a polymer blend with other polymers, such as cellulose ethers, thermoplastic starch, poly(vinyl alcohol), and the like. Generally any additive or filler of the art can be used with the copolyesters of the present invention.
The aliphatic-aromatic copolyesters which incorporate isosorbide of the present invention are useful within a wide variety of shaped biodegradable articles. The copolyesters may be solution or melt processed to form coatings, films and the like. Coatings may be produced by coating a substrate with polymer solutions of the copolyesters followed by drying, by coextruding the copolyesters with other materials, or by melt coating a preformed substrate with the polyesters of the present invention. The coatings derived from the copolyesters of the present invention have utility as barriers to moisture, oxygen, carbon dioxide and the like. The coatings derived from the copolyesters of the present invention also are useful as adhesives. Films of the copolyesters of the present invention may be produced by any known art method, including, for example, solution or melt casting.
Shaped articles include films, sheets, fibers, melt blown containers, molded parts, such as cutlery, foamed parts, polymeric melt extrusion coatings onto substrates, polymeric solution coatings onto substrates, and the like. The copolyesters may be solution or melt processed to form coatings, films and the like. Films of the copolyesters of the present invention may be produced by any known art method, including, for example, solution or melt casting.
Film or sheets are made from the polymer of the invention by any process known in the art. The difference between a film and a sheet is the thickness, but there is no set industry standard as to when a film becomes a sheet.
For purposes of this invention, a film is less than or equal to about 0.25 mm (10 mils) thick, preferably between about 0.025 mm and 0.15 mm (1 mil and 6 mils). However, thicker films can be formed up to a thickness of about 0.50 mm (20 mils).
The film of the present invention can be formed by either solution casting or extrusion as known in the art. Extrusion is particularly preferred for formation of xe2x80x9cendlessxe2x80x9d products, such as films and sheets, which emerge as a continuous length. In extrusion, the polymeric material, whether provided as a molten polymer or as plastic pellets or granules, is fluidized and homogenized. This mixture is then forced through a suitably shaped die to produce the desired cross-sectional film shape. The extruding force may be exerted by a piston or ram (ram extrusion), or by a rotating screw (screw extrusion), which operates within a cylinder in which the material is heated and plasticized and from which it is then extruded through the die in a continuous flow. Single screw, twin screw, and multi-screw extruders may be used as known in the art. Different kinds of die are used to produce different products, such as blown film (formed by a blow head for blown extrusions), sheets and strips (slot dies) and hollow and solid sections (circular dies). In this manner, films of different widths and thickness may be produced, and, in some cases, such as when film is used as a coating, it may be extruded directly onto the object to be coated. For example, wires and cables can be sheathed directly with polymeric films extruded from oblique heads. As a further example, laminated paper coatings can be produced by melt extruding the polymer directly onto paperboard. After extrusion, the polymeric film is taken up on rollers, cooled and taken off by means of suitable devices which are designed to prevent any subsequent deformation of the film.
Using extruders as known in the art, film can be produced by extruding a thin layer of polymer over chilled rolls and then further drawing down the film to size by tension rolls. Preferably, the finished film is less than or equal to about 0.25 mm thick. Blown film, which is generally stronger, tougher, and made more rapidly than cast film, is made by extruding a tube. In producing blown film, the melt flow is turned upward from the extruder and fed through an annular die. As this tube leaves the die, internal pressure is introduced through the die mandrel with air, which expands the tube from about 1.5 to about 2.5 times the die diameter and simultaneously draws the film, causing a reduction in thickness. The resulting sleeve is subsequently slit along one side, making a larger film width than could be conveniently made via the cast film method. In extrusion coating, the substrate (paper, foil, fabric, polymeric film, and the like) is compressed together with the extruded polymeric melt by pressure rolls so that the polymer impregnates the substrate for maximum adhesion.
For manufacturing large quantities of film, a sheeting calendar can be employed. The rough film is fed into the gap of the calendar, a machine comprising a number of heatable parallel cylindrical rollers which rotate in opposite directions and spread out the polymer and stretch it to the required thickness. The last roller smoothes the film thus produced. If the film is required to have a textured surface, the final roller is provided with an appropriate embossing pattern. Alternatively, the film may be reheated and then passed through an embossing calendar. The calendar is followed by one or more cooling drums. Finally, the finished film is reeled up.
Alternatively, as mentioned previously, a supporting material may be coated directly with a film. For example, textile fabrics, paper, cardboard, metals, various building materials and the like, may be coated directly with the polyester polymer for the purpose of electrical insulation, protection against corrosion, protection against the action of moisture or chemicals, impermeability to gases and liquids, or increasing the mechanical strength. One process to achieve this is referred to as melt extrusion of the polymeric melt onto a substrate. Coatings are applied to textiles, foil, and other sheet materials by continuously operating spread-coating machines. A coating knife, such as a xe2x80x9cdoctor knifexe2x80x9d, ensures uniform spreading of the coating materials (in the form of solution, emulsions, or dispersions in water or an organic medium) on the supporting material, which is moved along by rollers. The coating is then dried. Alternatively, when the coating is applied to the supporting material in the form of a polymeric film, the process is called laminating.
Metal articles of complex shapes can also be coated with the polymeric film by the whirl sintering process. The articles, heated to above the melting point of the polymer, are introduced into a fluidized bed of powdered polymer wherein the polymer particles are held in suspension by a rising stream of air, thus depositing a coating on the metal by sintering.
Extruded films may also be used as the starting material for other products. For example, the film may be cut into small segments for use as feed material for other processing methods, such as injection molding.
The extrusion process can be combined with a variety of post-extruding operations for expanded versatility. Such post-forming operations include altering round to oval shapes, blowing the film to different dimensions, machining and punching, biaxial stretching and the like, as known to those skilled in the art.
The polymeric film of the invention may be combined with other polymeric materials during extrusion and/or finishing to form laminates or multilayer films with improved characteristics, such as water vapor resistance. In particular, the polymeric film of the invention may be combined with one or more of the following: poly(ethylene terephthalate) (PET), aramid, polyethylene sulfide (PES), polyphenylene sulfide (PPS), polyimide (PI), polyethylene imine (PEI), poly(ethylene naphthalate) (PEN), polysulfone (PS), polyether ether ketone (PEEK), olefins, polyethylene, poly(cyclic olefins), cellulose, and cyclohexylene dimethylene terephthalate, for example. A multilayer or laminate film may be made by any method known in the art, and may have as many as five or more separate layers joined together by heat, adhesive and/or tie layer, as known in the art.
A film may also be made by solution casting, which produces more consistently uniform gauge film than that made by melt extrusion. Solution casting comprises dissolving polymeric granules, powder or the like in a suitable solvent with any desired formulant, such as a plasticizer or colorant. The solution is filtered to remove dirt or large particles and cast from a slot die onto a moving belt, preferably of stainless steel, dried, whereon the film cools. The extrudate thickness is five to ten times that of the finished film. The film may then be finished in a like manner to the extruded film.
Regardless of how the film is formed, it is desirably subjected to biaxial orientation by stretching in both the machine and transverse direction after formation. The machine direction stretch is initiated in forming the film simply by rolling out and taking up the film. This inherently stretches the film in the direction of takeup, orienting some of the fibers. Although this strengthens the film in the machine direction, it allows the film to tear easily in the direction at right angles because all of the fibers are oriented in one direction.
Biaxial stretching orients the fibers parallel to the plane of the film, but leaves the fibers randomly oriented within the plane of the film. This provides superior tensile strength, flexibility, toughness and shrinkability, for example, in comparison to non-oriented films. It is desirable to stretch the film along two axes at right angles to each other. This increases tensile strength and elastic modulus in the directions of stretch. It is most desirable for the amount of stretch in each direction to be roughly equivalent, thereby providing similar properties or behavior within the film when tested from any direction. However, certain applications, such as those desiring a certain amount of shrinkage or greater strength in one direction over another, as in labels or adhesive and magnetic tapes, will require uneven, or uniaxial, orientation of the fibers of the film.
The biaxial orientation may be obtained by any process known in the art. However, tentering is preferred, wherein the material is stretched while heating in the transverse direction simultaneously with, or subsequent to, stretching in the machine direction.
Shrinkage can be controlled by holding the film in a stretched position and heating for a few seconds before quenching. This heat stabilizes the oriented film, which then may be forced to shrink only at temperatures above the heat stabilization temperature.
The above process conditions and parameters for film making are determined by a skilled artisan for any given polymeric composition and desired application.
The properties exhibited by a film will depend on several factors including the polymeric composition, the method of forming the polymer, the method of forming the film, and whether the film was treated for stretch or biaxially oriented. These factors affect many properties of the film, such as shrinkage, tensile strength, elongation at break, impact strength, dielectric strength and constant, tensile modulus, chemical resistance, melting point, heat deflection temperature, and the like.
The film properties may be further adjusted by adding certain additives and fillers to the polymeric composition, such as colorants, dyes, UV and thermal stabilizers, antioxidants, plasticizers, lubricants antiblock agents, slip agents, and the like, as recited above. Alternatively, the copolyesters of the present invention may be blended with one or more other polymers, such as starch, to improve certain characteristics.
The biodegradable films of the present invention can be used e.g., in packaging, especially of foodstuff, adhesives, insulators, capacitors, photographic development, x-ray development, and as laminates. For many of these uses, the heat resistance of the film is an important factor. Thus, the higher melting point and Tg of the present polyesters are desirable.
The present invention also includes biodegradable shaped articles in the form of sheets produced from aliphatic-aromatic copolyesters.
Biodegradable polymeric sheets have a variety of uses, such as in signage, glazings, thermoforming articles, displays and display substrates, for example. For many of these uses, the heat resistance of the sheet is an important factor. Therefore, a higher melting point and glass transition temperature are desirable to provide better heat resistance and greater stability. Further, it is desired that these sheets have ultraviolet (UV) and scratch resistance, good tensile strength, high optical clarity, and a good impact strength, particularly at low temperatures.
The copolyesters of the present invention may be formed by one of the above methods, or by any other method known in the art, they may be formed into sheets directly from the polymerization melt. In the alternative, the copolyester may be formed into an easily handled shape (such as pellets) from the melt, which may then be used to form a sheet. The sheet of the present invention can be used for forming signs, glazings (such as in bus stop shelters, sky lights or recreational vehicles), displays, automobile lights and in thermoforming articles, for example.
The difference between a sheet and a film is the thickness, but there is no set industry standard as to when a film becomes a sheet. For purposes of this invention, a sheet is greater than about 0.25 mm (10 mils) thick, preferably between about 0.25 mm and 25 mm, more preferably from about 2 mm to about 15 mm, and even more preferably from about 3 mm to about 10 mm. In a preferred embodiment, the sheets of the present invention have a thickness sufficient to cause the sheet to be rigid, which generally occurs at about 0.50 mm and greater, However, sheets greater than 25 mm, and thinner than 0.25 mm may be formed. Sheets may be formed by any process known in the art, such as extrusion, solution casting or injection molding. The parameters for each of these processes can be determined by one of ordinary skill in the art depending upon viscosity characteristics of the copolyester and the desired thickness of the sheet.
The sheet of the present invention is preferably formed by either solution casting or extrusion. Extrusion is particularly preferred for formation of xe2x80x9cendlessxe2x80x9d products, such as films and sheets, which emerge as a continuous length. For example, see applications WO 96/38282 and WO 97/00284, which describe the formation of crystallizable sheets by melt extrusion.
In extrusion, the polymeric material, whether provided as a molten polymer or as plastic pellets or granules, is fluidized and homogenized. This mixture is then forced through a suitably shaped die to produce the desired cross-sectional sheet shape. The extruding force may be exerted by a piston or ram (ram extrusion), or by a rotating screw (screw extrusion), which operates within a cylinder in which the material is heated and plasticized and from which it is then extruded through the die in a continuous flow. Single screw, twin screw, and multi-screw extruders may be used as known in the art. Different kinds of die are used to produce different products, such as sheets and strips (slot dies) and hollow and solid sections (circular dies). In this manner, sheets of different widths and thickness may be produced. After extrusion, the polymeric sheet is taken up on rollers, cooled and taken off by a suitable devices which are designed to prevent any subsequent deformation of the sheet.
Using extruders as known in the art, a sheet can be produced by extruding a thin layer of polymer over chilled rolls and then further drawing down the sheet to size by tension rolls. Preferably, the finished sheet is greater than 0.25 mm thick.
For manufacturing large quantities of sheets, a sheeting calendar can be employed. The rough film is fed into the gap of the calendar, a machine comprising a number of heatable parallel cylindrical rollers which rotate in opposite directions and spread out the polymer and stretch it to the required thickness. The last roller smoothes the sheet thus produced. If the sheet is required to have a textured surface, the final roller is provided with an appropriate embossing pattern. Alternatively, the sheet may be reheated and then passed through an embossing calendar. The calendar is followed by one or more cooling drums. Finally, the finished sheet is reeled up.
The above extrusion process can be combined with a variety of post-extruding operations for expanded versatility. Such post-forming operations include altering round to oval shapes, stretching the sheet to different dimensions, machining and punching, biaxial stretching and the like, as known to those skilled in the art.
The polymeric sheet of the invention may be combined with other polymeric materials during extrusion and/or finishing to form laminates or multilayer sheets with improved characteristics, such as water vapor resistance. These are discussed above with reference to films.
A sheet may also be made by solution casting as discussed above.
Further, sheets and sheet-like articles, such as discs, may be formed by injection molding by any method known in the art.
Shrinkage can be controlled by holding the sheet in a stretched position and heating for a few seconds before quenching. This heat stabilizes the oriented sheet, which then may be forced to shrink only at temperatures above the heat stabilization temperature.
The above process conditions and parameters for sheet making can be determined by a skilled artisan for any given polymeric composition and desired application.
The properties exhibited by a sheet will depend on several factors including the polymeric composition, the method of forming the polymer, the method of forming the sheet, and whether the sheet was treated for stretch or biaxially oriented. These factors affect many properties of the sheet, such as shrinkage, tensile strength, elongation at break, impact strength, dielectric strength and constant, tensile modulus, chemical resistance, melting point, heat deflection temperature, and the like.
The sheet properties may be further adjusted by adding certain additives and fillers to the polymeric composition, such as colorants, dyes, UV and thermal stabilizers, antioxidants, plasticizers, lubricants antiblock agents, slip agents, and the like, as recited above. Alternatively, the copolyesters of the present invention may be blended with one or more other polymers, such as starch, to improve certain characteristics. Other polymers may be added to change such characteristics as air permeability, optical clarity, strength and/or elasticity, for example.
The sheets of the present invention may be thermoformed by any known method into any desirable shape, such as covers, skylights, shaped greenhouse glazings, displays, food trays, and the like. The thermoforming can be accomplished by heating the sheet to a sufficient temperature and for sufficient time to soften the copolyester so that the sheet can be easily molded into the desired shape. In this regard, one of ordinary skill in the art can determine the optimal thermoforming parameters depending upon the viscosity and crystallization characteristics of the polyester sheet.
A further specific aspect of the present invention includes biodegradable shaped articles in the form of containers produced from the copolyesters. The containers may be made by any method known in the art, such as extrusion, injection molding, injection blow molding, rotational molding, thermoforming of a sheet, and stretch-blow molding.
A preferred method for molding a container is stretch-blow molding. In this case, use may be made of any of the cold parison methods, in which a preformed parison (generally made by injection molding) is taken out of the mold and then subjected to stretch blow molding in a separate step. The hot parison method as known in the art may also be used, wherein the hot parison is immediately subjected to stretch blow molding in the same equipment without complete cooling after injection molding to make the parison. The parison temperature will vary based on the composition of the polymer to be used. Generally, parison temperatures in the range from about 90xc2x0 to about 160xc2x0 C. are found useful. The stretch blow molding temperature will also vary dependant on the material composition used, but a mold temperature of about 80xc2x0 C. to about 150xc2x0 C. is generally found to be useful.
Containers of the invention may have any shape desirable, and particularly include narrow-mouth bottles and wide-mouth bottles having threaded tops and a volume of about 400 mL to about 3 liters, although smaller and larger containers may be formed.
The containers can be used in standard cold fill applications. For some of the compositions of the present invention, hot fill applications may also be used.
The containers of the invention are suitable for foods and beverages, and other solids and liquids. The containers are normally clear and transparent, but can be modified to have color or to be opaque, rather than transparent, if desired, by adding colorants or dyes, or by causing crystallization of the polymer, which results in opaqueness.
A further specific aspect of the present invention includes biodegradable shaped articles in the form of fiber produced from the aliphatic-aromatic copolyesters which incorporate isosorbide.
Polyester fibers are produced in large quantities for use in a variety of applications. In particular, these fibers are desirable for use in textiles, particularly in combination with natural fibers such as cotton and wool. Clothing, rugs, and other items may be fashioned from these fibers. Further, polyester fibers are desirable for use in industrial applications due to their elasticity and strength. In particular, they are used to make articles such as tire cords and ropes.
The term xe2x80x9cfibersxe2x80x9d as used herein is meant to include continuous monofilaments, non-twisted or entangled multifilament yams, staple yarns, spun yarns, and non-woven materials. Such fibers may be used to form uneven fabrics, knitted fabrics, fabric webs, or any other fiber-containing structures, such as tire cords.
The monomer composition of the copolyester of the present invention when used in fiber is desirably chosen to result in a partially crystalline polymer. The crystallinity is desirable for the formation of fibers, providing strength and elasticity. As first produced, the polyester is mostly amorphous in structure. In preferred embodiments, the polyester polymer readily crystallizes on reheating and/or extension of the polymer.
Fibers are made from the polymer by any process known in the art. Generally, melt spinning is preferred. Melt spinning comprises heating the polymer to form a molten liquid, or melting the polymer against a heated surface. The molten polymer is forced through a spinneret with a plurality of fine holes. Upon contact with air or a non-reactive gas stream after passing through the spinneret, the polymer solution from each spinneret solidifies into filaments. The filaments are gathered together downstream from the spinneret by a convergence guide, and may be taken up by a roller or a plurality of rollers. This process allows filaments of various sizes and cross sections to be formed, including filaments having a round, elliptical, square, rectangular, lobed or dog-boned cross section, for example.
Following the extrusion and uptake of the fiber, the fiber is usually drawn, thereby increasing the crystallization and maximizing desirable properties such as orientation along the longitudinal axis, which increases elasticity, and strength. The drawing may be done in combination with takeup by using a series of rollers, some of which are generally heated, as known in the art, or may be done as a separate stage in the process of fiber formation.
The polymer may be spun at speeds of from about 600 to 6000 meters per minute or higher, depending on the desired fiber size. For textile applications, a fiber with a denier per filament of from about 0.1 to about 100 is desired. Preferably, the denier is about 0.5 to 20, more preferably 0.7 to 10. However, for industrial applications the fiber should be from about 0.5 to 100 denier per filament, preferably about 1.0 to 10.0, most preferably 3.0 to 5.0 denier per filament. The required size and strength of a fiber can be readily be determined by one of ordinary skill in the art for any given application.
The resulting filamentary material is amenable to further processing through the use of additional processing equipment, or it may be used directly in applications requiring a continuous filament textile yarn. If desired, the filamentary material subsequently may be converted from a flat yarn to a textured yarn through known false twist texturing conditions or other processes known in the art. In particular, it is desirable to increase the surface area of the fiber to provide a softer feel and to enhance the ability of the fibers to breathe, thereby providing better insulation and water retention in the case of textiles, for example. The fibers may therefore be crimped or twisted by the false twist method, air jet, edge crimp, gear crimp, or stuffer box, for example. Alternatively, the fibers may be cut into shorter lengths, called staple, which may be processed into yarn. A skilled artisan can determine the best method of crimping or twisting based on the desired application and the composition of the fiber.
After formation, the fibers are finished by any method appropriate to the desired final use. In the case of textiles, this may include dyeing, sizing, or addition of chemical agents such as anitstatic agents, flame retardants, UV light stabilizers, antioxidants, pigments, dyes, stain resistants, antimicrobial agents and the like, which are appropriate to adjust the look and hand of the fibers. For industrial applications, the fibers may be treated to impart additional desired characteristics such as strength, elasticity or shrinkage, for example.
The continuous filament fiber of the invention may be used either as produced or texturized for use in a variety of applications such as textile fabrics for apparel and home furnishings, for example. High tenacity fiber can be used in industrial applications such as high strength fabrics, tarpaulins, sail cloth, sewing threads and rubber reinforcement for tires and V-belts, for example.
The staple fiber of the invention may be used to form a blend with natural fibers, especially cotton and wool. In particular, the polyester is a chemically resistant fiber which is generally resistant to mold, mildew, and other problems inherent to natural fibers. The polyester fiber further provides strength and abrasion resistance and lowers the cost of material. Therefore, it is ideal for use in textiles and other commercial applications, such as for use in fabrics for apparel, home furnishings and carpets.
Further, the polyester polymer of the invention may be used with another synthetic or natural polymer to form heterogenous fiber, thereby providing a fiber with improved properties. The heterogeneous fiber may be formed in any suitable manner, such as side-by-side, sheath-core, and matrix designs, as is known within the art.
A further specific aspect of the present invention includes biodegradable shaped foamed articles produced from the aliphatic-aromatic copolyesters which incorporate isosorbide.
The polyesters of the present invention may be readily foamed by a wide variety of methods known in the art. These include the injection of an inert gas such as nitrogen or carbon dioxide into the melt during extrusion or molding operations. Alternatively, inert hydrocarbon gases such as methane, ethane, propane, butane, and pentane, or chlorofluorocarobons, hydrochlorofluorocarbons, hydrofluorocarbons, and the like may be used. Another method involves the dry blending of chemical blowing agents with the polyester and then extruding or molding the compositions to provide foamed articles. During the extrusion or molding operation, an inert gas such as nitrogen is released from the blowing agents and provides the foaming action. Typical blowing agents include azodicarbonamide, hydrazocarbonamide, dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazodicarboxylate, 5-phenyl-3,6-dihydro-1,3,4-oxa-diazin-2-one, sodium borohydride, sodium bicarbonate, 5-phenyltetrazole, p,pxe2x80x2-oxybis(benzenesulfonylhydrazide) and the like. Still another method involves the blending of sodium carbonate or sodium bicarbonate with one portion of the polyester pellets, blending of an organic acid, such as citric acid, with another portion of the polyester pellets and then blending of the two types of pellets through extrusion or molding at elevated temperatures. Carbon dioxide gas is released from the interaction of the sodium carbonate and citric acid to provide the desired foaming action in the polymeric melt.
It is often desirable that the foamable polyester compositions incorporate nucleation agents to create sites for bubble initiation, influence the cell size of the foamed sheet or object and to hasten the soldification of the as foamed article. Examples of said nucleation agents include sodium acetate, talc, titanium dioxide, polyolefin materials such as polyethylene, polypropylene, and the like.
As described above, the foamable polyester compositions may include a wide variety of additives, fillers, or be blended with other materials. For biodegradable foams, the addition of cellulose, cellulose derivatives, such as chemically modified cellulose, starch, and starch derivatives, such as chemically modified starch and thermoplastic starch, is especially preferred.
The following Examples are presented to illustrate the preparation and properties of the copolyester polymers of the invention. Comparative Examples are described, i.e., CE1, CE2, CE3 and CE4. Prophetic Examples E1-E21 describe copolyesters and copolymerization methods of the invention as well as the expected biodegradable and mechanical properties of the copolyesters of the invention.


A ratchet wrench includes a handle, a drive head, a ratchet wheel, a pawl member, a control knob, a positioning plate, and an urging spring. Thus, the ratchet wrench includes a positioning plate to push the pawl member, thereby reducing the volume of the ratchet wrench efficiently. In addition, the urging spring is supported and guided by the guide shaft of the positioning plate, so that the positioning plate is not easily deformed, thereby facilitating movement of the urging spring in the positioning plate.

1. Field of the Invention
The present invention relates to a ratchet wrench, and more particularly to a ratchet wrench, wherein the urging spring is supported and guided by the guide shaft of the positioning plate, thereby facilitating operation of the ratchet wrench.
2. Description of the Related Art
A conventional ratchet wrench in accordance with the prior art shown in FIGS. 1 and 2 comprises a handle 10, a drive head 15 mounted on a distal end of the handle 10 and having a first end formed with a receiving hole 16, a mediate portion formed with a receiving recess 17 communicating with the receiving hole 16, and a second end formed with a receiving chamber 18 communicating with the receiving recess 17, a ratchet wheel 20 mounted in the receiving hole 16 of the drive head 15 by a C-shaped snap 22 and having a periphery formed with a plurality of ratchet teeth 21, a pawl member 23 pivotally mounted in the receiving recess 17 of the drive head 15 and having a first side formed with a plurality of engaging teeth 24 engaged with the ratchet teeth 21 of the ratchet wheel 20 and a second side formed with an positioning edge 25, and a control knob 26 rotatably mounted in the receiving chamber 18 of the drive head 15 and formed with a hole 27 for receiving a spring 28 which is biased by an urging pin 29 which is urged on the positioning edge 25 of the pawl member 23 to push the pawl member 23 to press the ratchet wheel 20 to control the drive direction of the ratchet wheel 20. Thus, by rotation of the control knob 26, the ratchet wheel 20 is rotated in one direction only when the drive head 15 is rotated.
However, the conventional ratchet wrench needs a larger space to receive the urging pin 29, thereby increasing the volume of the ratchet wrench efficiently. In addition, the spring 28 is not supported by the control knob 26 efficiently, so that operation of the conventional ratchet wrench is not smooth and conveniently.

This patent is subject to a terminal disclaimer.


A personal design system according to the present invention designs the appearance of an equipment suiting the sensibility and the physical features of a user by establishing data communication between a user terminal comprising a user information inputting section and a server on the side of a producer. The user inputs user information such as the sensibility and the physical features of the user corresponding to the designed appearance of the equipment using the user information inputting section. The equipment having the designed appearance intended by the user is produced on the basis of the inputted user information and a database provided in the server by designing means provided in the user terminal.

1. Field of the Invention
The present invention relates generally to a CAD (Computer Aided Design) system, and more particularly, to a personal design system to which input can be simply provided for a general consumer and a personal equipment production system for actually producing an equipment having an appearance designed in the personal design system.
2. Description of the Prior Art
In recent years, as a CAD system, ones for an engineer having a certain degree of skill such as a two-dimensional CAD and a three-dimensional CAD have spread. However, the production of appearance of an equipment by a conventional CAD system requires complicated operations, whereby the CAD system is difficult for a general consumer which is not a specialist to handle.
In recent years, therefore, a device so adapted as to design the appearance of an equipment on the basis of an inputted word representing a user's intention (hereinafter referred to as a sensible word) has been proposed in the design of a front door, for example (see Japanese Patent Laid-Open No. 103347/1994).
However, the above-mentioned conventional equipment appearance design device is merely an equipment appearance design support device, and has the disadvantage in that it is difficult to construct a large-scale database required to cope with sensible words inputted by a variety of users.
Furthermore, the conventional equipment appearance design device only displays an image with respect to input of a sensible word representing a user's intention. Particularly when a user visually recognizes an equipment or the like displayed in a three-dimensional manner and desires to further input a sensible word, it is difficult for the user to suitably express an image intended by himself and herself with respect to the equipment displayed on a display screen in a three-dimensional manner. In addition, it takes long to change three-dimensional data on the basis of the inputted sensible word and display the equipment on the display screen in a three-dimensional manner, whereby it takes long to input the sensible word.
Furthermore, the above-mentioned equipment appearance design device cannot evaluate the ease of use in a certain use environment of an equipment having a designed appearance, for example, the interior and the exterior of a house, a living room and a bedroom even in the same house, and the morning and the night even in the same living room.
On the other hand, it is considered that an electronic/mechanical equipment spreading on the market is produced using the above-mentioned conventional CAD system by an engineer on the side of a producer (a corporation) manufacturing products. The electric/mechanical equipment is produced in accordance with a predetermined standard such as the taste or the physical features of a standard person. Consequently, an electronic/mechanical equipment (for example, a shape and a pattern) suiting the taste and the physical features of each user is hardly produced and sold. In recent years, with diversifying desires of users, the provision of an electronic/mechanical equipment reflecting a shape, a color and a pattern conforming to an image (sensibility) required by a user has been paid attention to.
In order to provide an electrical/mechanical equipment based on the design of an appearance conforming to an image (sensibility) required by a user, a system for producing the electronic/mechanical equipment on the basis of the design of the appearance intended by the user is required. That is, in order to satisfy the above-mentioned requirement, a system for performing a series of processing from the design of the appearance of the equipment conforming to the user's intention to the production of the electronic/mechanical equipment is required.
The present invention has been made in view of the above-mentioned prior art and has for its object to provide a personal design system which is very simple to handle and can design the appearance of an equipment suiting the sensibility and the physical features of a consumer by establishing data communication.
Another object of the present invention is to provide a personal equipment production system for producing an equipment on the basis of its appearance designed in conformity to a consumer's intention.
Still another object of the present invention is to provide a personal design system capable of shortening time to input an image (sensibility) intended by a user and capable of making it easy to extract a user's intention.
A further object of the present invention is to provide a personal equipment production system for estimating facility and the like of a designed equipment, corresponding to the environment in which the equipment is used.

Personal design system and personal equipment production system for actually producing equipment having designed appearance


An image pickup device has a plurality of photoelectric converter substrates carrying respective input/output terminals connected to the photoelectric converters. The device comprises leads connected to the input/output terminals and extending to the side opposite to the light receiving surfaces of the photoelectric converter substrates thorough the gaps separating the substrates.

1. Field of the Invention
This invention relates to an image pickup device, a radiation image pickup device and an image processing system. More particularly, the present invention relates to a radiation image pickup device adapted to extend the image pickup area and an image processing system using such a radiation image pickup device. For the purpose of the invention, radiation refers to α rays, β rays, γ rays and so on and includes X-rays.
2. Related Background Art
A film screen system realized by combining intensifying screens and an X-ray film is popularly used for X-ray photography for the purpose of medical diagnosis. With such a system, the X-rays transmitted through an object to be photographed contain information on the inside of the object and are converted into rays of visible light showing intensities proportional to those of the transmitted X-rays by the intensifying screens. Then, the X-ray film is exposed to the rays of visible light.
In recent years, X-ray digital image pickup devices have been marketed. With such X-ray digital image pickup devices, X-rays are converted into rays of visible light with intensities proportional to those of the original X-rays by means of a scintillator and then the obtained rays of visible light are converted into an electric signal by means of a photoelectric converter, which electric signal is then transformed into a digital signal by means of an A/D converter.
More specifically, a known type of X-ray digital image pickup device comprises an ordinary image pickup device formed by arranging elements on a glass substrate, each element having an amorphous semiconductor sandwiched between a pair of electrodes, and a scintillator laid on the image pickup device in order to convert X-rays into rays of visible light. Another known type of X-ray digital image pickup device is realized by two-dimensionally linking modules, each comprising a tapered optical fiber formed by heating and softening a bundle of optical fibers and drawing the softened bundle, a photoelectric converter such as a CCD arranged at the tapered side of the optical fiber and a scintillator laid on the opposite side of the optical fiber.
X-ray digital image pickup devices of the above described types are mostly used for medical diagnosis and other applications. Such a device is required to show a high resolution, a low noise level, an ability of producing moving images and a wide imaging angle so that the doctor may be able to detect the diseased area quickly and make an accurate diagnosis.
However, while X-ray digital image pickup devices comprising amorphous semiconductors typically made of silicon and arranged on a glass substrate are adapted to show a large sensor effective area, they are accompanied by problems including that the size of pixels cannot be reduced because of the manufacturing process and the device characteristics and that the device sensitivity is limited. Therefore, devices of this type are not adapted to high speed operation particularly in terms of displaying moving images.
On the other hand, X-ray digital image pickup devices comprising photoelectric converters such as CCDs realized by using a silicon substrate have a problem that they cannot show a large sensor effective area mainly because of the restrictions in the manufacturing process and the high power consumption level that produces heat, although they are adapted to realize a small pixel size and pick up moving images because they are highly sensitive and can be driven at high speed.
There has been proposed a device comprising an increased number of elements, using optical fibers tapered in such a way that non-sensor areas of the photoelectric converters may not overlap in order to make it show an enlarged sensor effective area. FIG. 1 of the accompanying drawings is a schematic illustration of some of the photoelectric converters of such a device. In FIG. 1, there are shown substrates 1 carrying respective photoelectric converters, scintillators 3 for converting X-rays into rays of visible light showing a wavelength that can be detected by the photoelectric converters, a base member 7, tapered optical fibers 8, protection glass plates 9 and bonding wires 11. Reference numeral 12 in FIG. 1 denotes a ceramic package.
However, a tapered optical fiber is costly and the ratio of dimensional reduction is not stable because the tapering process involves dimensional dispersions. Furthermore, while several tapered optical fibers that are thick and heavy may be linked together, it is not realistic to link a large number of tapered optical fibers in order to produce a sensor effective area necessary for imaging the chest of a subject. Additionally, tapered optical fibers show a poor light transmission factor to a great disadvantage of the device.
FIG. 2 of the accompanying drawings is a schematic illustration of a conventional X-ray moving image system using an image intensifier (I—I). In FIG. 2, reference numeral 16 denotes the I—I. The X-rays striking the light entering surface are converted into electrons, which are multiplied to realize a high sensitivity of the system. The electrons are then converted to rays of light at the light exiting surface to show an image, which is then input to a CCD camera 15.
However, a system comprising such an image intensifier (I—I) inevitably shows large dimensions because it comprises a vacuum tube.
In the case of a CCD image pickup device, peripheral circuits and electrodes are required to be located in areas outside the display pixel area to inevitably make the peripheral marginal area surrounding the effective display area large as shown in FIG. 3A of the accompanying drawings. Additionally, the X-ray image sensor itself faces a limit for downsizing.
X-ray image sensors that are used for dental diagnosis are designed to be put into the mouth of the patient in order to pick up an image of the inside of the mouth. Then, however, it is impossible to take a picture of some of the molar teeth with such an X-ray image sensor. Particularly, it is highly difficult to put such an X-ray image sensor into the mouth of a child and, if such a sensor is forced into the mouth, it can induce a feeling of vomiting on the part of the patient to make the effort for taking a picture abortive.
As described above, it has been highly difficult to realize an X-ray digital image pickup device for medical diagnosis that is adapted to show a moving image with a high resolution if it is made to have a large sensor effective area and show reduced dimensions at low cost.

Image pickup device, radiation image pickup device and image processing system


A method performed by a network device may include obtaining an Internet Protocol address and a user device identifier associated with a user device, determining that the obtained user device identifier does not match a previous user device identifier associated with the obtained Internet Protocol address, and monitoring packets destined for the obtained Internet Protocol address to determine whether the packets are associated with a streaming application, based on determining that the obtained user device identifier does not match the previous user device identifier. The method may further include detecting a packet destined for the obtained Internet Protocol address, where the packet is associated with a streaming application and where the packet is received from a particular network device and signaling the particular network device to stop sending packets associated with the streaming application and destined for the obtained Internet Protocol address.

Mobile wireless communication devices continue to increase in popularity, leading to increasing numbers of users and to demands for more services and higher data rates. In order to satisfy the needs of users and to improve service, providers of mobile wireless communication services continue to improve wireless access networks used to deliver services for users of mobile communication devices. One aspect of such improvements may relate to management of streaming applications. A streaming application may provide real-time content to a user, such as real-time audio and/or video content. Managing data associated with streaming applications in a wireless network may prove to be quite challenging.

Dynamic mobile streaming application suppression


A clamping or chucking tool for clamping a test sample in a testing machine has a clamping housing for applying a wedging action to the sample with the aid of one or two clamping jaws that are activated by an operating member that is inserted into the clamping housing and axially displaceable in the clamping housing. The clamping jaws are slidingly guided in a V-groove of the operating member but are stationary in the axial direction of the clamping housing, while the operating member is movable axially relative to the clamping housing for imparting to the clamping jaws a radial movement component perpendicularly to the longitudinal axis of the test sample. Lateral guide arms engage respective guide grooves in the clamping jaws to hold the clamping jaws against axial movement while permitting the radial movement. The clamping housing and the operating member are provided with at least one lateral opening for a rapid insertion of the test sample laterally into the clamping housing. This type of construction provides a chucking tool for holding test samples that may be exposed to tension loads, or to compression loads and/or to torque loads.

Clamping devices with a wedging action are known in many different constructions. These constructions fall into three basic types. An open type, a closed type, and a semi-open type are recognized. Such clamping devices are also classified in accordance with the intended type of stress to be applied to a test sample, namely for applying tension stress or for applying compression stress, or for applying tension for compression stress as desired. The construction will differ for the type of stress to be applied to the test sample.
German Patent Publication DE-AS 2,141,566, for example, discloses a clamping device with a wedging action of the open type construction. Such a structure is used exclusively for testing samples with regard to tensile stress, whereby the samples must have either a circular or a rectangular flat cross-sectional configuration. This known clamping device with a wedging action, has a clamping housing with a wedge-shaped clamping mouth formed by respective wedge-shaped clamping elements referred to as wedging clamping jaws mounted in said clamping housing for an axial displacement. Due to the wedge shape of the clamping mouth and of the clamping jaws, the latter generate simultaneously with an axial movement a radially directed clamping movement. In order to apply the clamping action to a test sample, the clamping jaws are operated by a piston cylinder device in an axial direction. In order to again release a test sample from the clamping jaws, the piston cylinder device is depressurized. Tension springs are connected to the clamping jaws in such a way that they counteract the clamping force of the piston cylinder device, whereby the clamping jaws upon depressurizing the piston cylinder device, are returned by the tension springs into the starting position, thereby to release the clamping action.
It is also known from European Patent Publication No.: 0,257,104 to provide a piston cylinder device for opening the clamping jaws by causing a retraction movement of these clamping jaws. In such a structure the clamping housing is constructed so that the sample to be tested can be inserted into the clamping housing in a lateral direction. This feature speeds up and simplifies the clamping operation of the sample. The clamping jaws and the clamping housing in which these jaws are mounted, are so constructed that a self-locking feature of the wedges of the clamping jaws can be utilized by applying a tension force to the sample.
The just described so-called open type of construction of the wedging clamping device has the disadvantage that due to the forces that the clamping housing itself must take up when a sample is loaded, the clamping housing must have relatively large dimensions so as to avoid any elastic reaction of the clamping housing which may result in the release of the test sample. For example, German Utility Model Publication 1,977,205discloses a structure intended to minimize the elastic reaction of the clamping housing. In order to strengthen the clamping housing, a ring-shaped clamping piece is arranged around the clamping housing and the ring-shaped clamping piece is operable by a hydraulic drive.
U.S. Pat. No. 3,335,603 (Gram) discloses a wedge-type clamping device of the so-called closed construction capable of applying tension loads or compression loads to a test sample. This known clamping device comprises clamping wedges arranged in a housing closed on all sides, except for an axial inlet opening for permitting the insertion of the test sample end into the clamping device. Thus, it is a disadvantage of the closed type of construction that the sample must be inserted in the axial longitudinal direction which requires the axial displacement of at least one of the two clamping devices or clamping heads needed for holding a test sample. Such axial displacement is time consuming and requires additional structural features for performing the axial displacement. However, the closed type of construction has the advantage that it has a small overall structural height due to the closed type construction of the housing.
Another known clamping device is constructed particularly for applying a compression load to a sample. The construction is such that the compression force introduced into the test sample causes a closing of the wedges for applying the clamping action to the sample.

Chucking tool with a wedging action for testing machines


An object of the present invention is to provide a die suitable for producing an optical panel having an optical pattern (e.g. dots or lines) integrally formed on at least one side of the optical panel, which is, for example, an edge light panel or a light diffusion panel, which is used in a backlight or front light for a liquid crystal display, and various illuminators such as electric signs. According to the present invention, there are provided an optical-panel molding die for integrally forming an optical pattern on at least one side of an optical panel, which comprises a metal substrate and a molding pattern corresponding to said optical pattern and formed of a photosensitive heat-resistant resin on one side of the metal substrate, the whole of the surface having the molding pattern of the metal substrate being covered with a layer of said heat-resistant resin; a process for producing the die; and a process for producing an optical panel by using the die.

The present invention relates to a die used for producing an optical panel having an optical pattern (e.g. dots or lines) integrally formed on at least one side of the optical panel, which is, for example, an edge light panel or a light-diffusing panel, which is used in a backlight or front light for a liquid crystal display, and various illuminators such as electric signs; a process for producing the die; and a process for producing an optical panel by using the die.
Such an optical panel having an optical pattern formed on at least one side thereof is generally produced by injection molding of a transparent thermoplastic resin. For giving such an optical pattern integrally, there have been known, for example, a method using a mold having concavities and convexities corresponding to the optical pattern of a product which are formed on the predetermined surface of the cavity by machining (e.g. cutting or blasting), electrical discharge machining, etching or the like, and the method proposed in JP-A-9-222514 in which to the inner surface of the mold of an injection molding machine is attached a nickel thin die called stamper which has concavities and convexities corresponding to the optical pattern of a product and formed on the surface of the die, and is obtained by conducting nickel plating on an uneven surface formed by the use of a photoresist and then peeling the photoresist layer.
However, in the case of the mold subjected to machining (e.g. cutting or blasting), electrical discharge machining, etching or the like, the minimum size of the concavities and convexities formed is as large as at least hundreds micrometers. Therefore, the mold is disadvantageous in that when light is introduced into an optical panel injection-molded by the use of the mold, the contrast between light and darkness is too high owing to the pattern, so that it is difficult to obtain uniform light for illumination. On the other hand, the stamper made of nickel involves, for example, the following problems: a very long process is necessary for producing such a stamper; the unit cost of the stamper is high because its production entails high cost of material and running cost and requires a long time; and moreover the production is difficult because individual steps in the production are difficult, so that each of them requires experience and know-how.
The present inventors has found a technique for forming a molding pattern of a photosensitive heat-resistant resin directly on the surface of a metal substrate by a photoresist method using the photosensitive heat-resistant resin and has proposed the technique in JP-A-2001-337229. When this method is adopted, a die having a very precise optical pattern formed thereon can be obtained at a low cost in a short time. However, experiments after the proposal elucidated the following: the release properties in molding by the use of the die are not always good, so that it is necessary, for example, to increase cooling time in a mold a little, and the unsatisfactory release properties tends to affect the durability. SUMMARY OF THE INVENTION
The present inventors further investigated in order to solve such problems, and consequently found that when the whole of the surface of the metal substrate of a die which has a molding pattern made of a photosensitive heat-resistant resin and corresponding to an optical pattern is covered with said photosensitive heat-resistant resin, the release properties of a molded optical panel from the die is improved; and that when the surface of the metal substrate as a starting material for the die is previously roughened, the release properties and the durability of the die are further improved, whereby the present invention has been accomplished.
Therefore, an object of the present invention is to provide a die obtained by improving the molding die disclosed in JP-A-2001-337229, namely, to provide a die more suitable for producing an optical panel having an optical pattern (e.g. dots or lines) integrally formed on at least one side of surfaces of the optical panel, which is, for example, an edge light panel or a light diffusion panel, which is used in a backlight or front light for a liquid crystal display, and various illuminators such as electric signs; a process for producing the die; and a process for producing an optical panel by using the die.
According to the present invention, there is provided an optical-panel molding die for integrally forming an optical pattern on at least one side of surfaces of an optical panel, the die comprising a metal substrate and a molding pattern corresponding to said optical pattern and formed of a photosensitive heat-resistant resin on one side of surfaces of the metal substrate, wherein the whole of the surface having the molding pattern of the metal substrate is covered with a layer of said heat-resistant resin. In this molding die, it is advantageous to roughen previously the surface of the metal substrate which is to be covered with said heat-resistant resin.
In addition, according to the present invention, there is also provided a process for producing the above-mentioned optical-panel molding die which comprises the steps of forming a layer of a photosensitive heat-resistant resin on the surface of a metal substrate, exposing the layer of the photosensitive heat-resistant resin to light through a mask having a pattern corresponding to the optical pattern of the optical panel, and developing the layer to form a molding pattern corresponding to the pattern of the mask on the layer of the photosensitive heat-resistant resin, wherein the photosensitive heat-resistant resin is left all over the one side of surfaces of the metal substrate also after the development.
Specifically, it is possible to adopt a method in which the development is terminated before the complete dissolution of portions to be developed of the photosensitive heat-resistant resin, whereby the photosensitive heat-resistant resin is left also on areas of the metal substrate which correspond to the developed portions of the resin. It is also possible to adopt a method in which two layers of the photosensitive heat-resistant resin are formed on the surface of the metal substrate and the first layer is deprived of its photosensitivity after its formation, whereby the first layer having no photosensitivity is left on the metal substrate.
Furthermore, according to the present invention, there is provided a process for producing an optical panel having an optical pattern integrally formed on at least one side of surfaces of the optical panel, the process comprising the steps of setting, on at least one of the two surfaces of a mold, a molding die comprising a metal substrate and a molding pattern corresponding to the optical pattern of the optical panel and formed of a photosensitive heat-resistant resin on one side of surfaces of the metal substrate, the whole of the surface having the molding pattern of the metal substrate being covered with a layer of said heat-resistant resin; and injecting a transparent molten resin into a mold cavity comprising the molding die as at least one of its surfaces, to mold the resin.

Die for molding optical panel, process for production thereof, and use thereof


A toy flying discus is fabricated from a form sustaining, resilient, plastic foam material having a density which enables the discus to have an aerodynamic profile and sufficient mass to achieve distant flight with minimal launching force and to have sufficient resilience to absorb impact forces thereby preventing damage to objects which it contacts. The surface of the discus is absorbent to blend applied pigments for achieving an aesthetically pleasing appearance.

This invention relates to a toy discus of the type which can be used for playing a game of catch. More specifically, the invention relates to a toy discus which can be launched by a flick of the wrist to travel substantial distances, through the air along a curved flight path, for reaching a catcher at a desired position.
It is known in the art to fabricate a toy discus from a substantially rigid plastic material in the shape of a hollow dish. The walls of such toy discusses must be kept relatively thin to keep their overall weight low so as to minimize the possibility of injury to a person who may be hit by the flying toy. Too little weight in a toy discus interferes with its ability to overcome air resistance and limits the potential flight distance of the toy.
It is also known in the prior art to employ a toy discus made of a soft fabric material. Such toy discusses require that their circumferences have weights sewn into them in order to provide the necessary mass for enabling flight of the discus.
The use of rigid materials and/or weights in toy discusses makes them potentially injurious to persons and objects. For example, prior art toy discusses are wholly unsuitable to use indoors where there may be breakable objects such as windows or mirrors which cannot withstand the impact of a rigid toy.


An electrostatic toner image forming method is disclosed. In the method, the photoreceptor comprises a charge generation layer containing an N-type charge generation material and a charge transportation layer containing a charge transportation material and has a thickness of from 5 to 15 μm; and the toner contains colored particles which have a ratio, Dv50/Dp50, from 1.0 to 1.15 and a ratio, Dv75/Dp75, from 1.0 to 1.20 and the content of particles having a diameter of 0.7×Dp50 is not more than 10 in number, and the reversal development is performed under a condition satisfying the following expression;50≦|E|≦100 Expression 1                E: Electrical field intensity applied to the organic photoreceptor during development.

Recently, organic photoreceptors have been widely used as electrophotographic photoreceptors. Organic photoreceptors have advantages compared to other photoreceptors such as that a material suited for various exposure light sources emitting various wavelengths light from visible rays to infrared rays can be easily developed, a material with pollution potential to the environment can be selected and the production cost thereof is low. However it also has drawbacks such as that the mechanical strength and chemical resistively are low and tending of degradation of the static property, and on the surface is easily damaged.
Electrical and mechanical stress is applied directly to the organic photoreceptor, hereinafter simply referred to as photoreceptor, by a charging means, a developing means and a cleaning means. Accordingly, resisting ability against the stress is required of the photoreceptor.
Furthermore, resistivity to counter abrasion and often damage as well as degradation caused by reactive oxygen such as ozone and nitrogen oxide generated during corona discharge is required of the photoreceptor.
A constitution of the photoreceptor is frequently employed to overcome such mechanical and chemical resistivity problems in which the organic photoreceptor is constituted by series of layers of a charge generation layer and a charge transportation layer, in which the charge transportation layer as the surface layer is made of a uniform layer having high strength and high resistivity against permeation of the reactive gas, and the thickness of the charge transportation layer is not less than 20 μm.
Another investigated approach to overcome the problems is a method which provides a protective layer having high strength on the surface of the photoreceptor, as disclosed in JP-A 6-118681. However, such methods to increase the thickness of the charge transportation layer or to provide a stronger protective layer causes problems of image sharpness since the carriers generated in the charge generation are diffused to the sides before arriving at the surface. In the field of digital copying machines, formation a high resolution image is required to meat the demand of high image quality. However, a suitable static latent image can not be obtained by such a layer structure, or in the presence the protective layers causing diffusion of the carriers.
It is necessary for high fidelity reproduction to sufficiently maintain the potential contrast between the exposed and the unexposed areas of the photoreceptor. It is also important to inhibit the diffusion of generated carriers before the arrival at the surface charge for reproducing the high fidelity image. When the ratio D/μ of the diffusion constant D to the drift mobility μ in the charge transportation layer is large, the effect of the diffusion on the degradation of the high density static latent image must be taken into argument. Consequently the degradation of the static latent image is increased when the thickness of the charge transportation layer is increased, as disclosed in "Nihon Gazou Gakkai Shi (Journal of Image Society of Japan)" Vol. 38. No. 4, p. 296.
A photoreceptor in which the thickness of the charge transportation layer is reduced to inhibit diffusion of the static latent image has been proposed, as disclosed in JP-A 5-119503. However, in practice an unclear image with lowered image density tends to form when an image is formed by employing an image forming apparatus in which such a proposed organic photoreceptor is used. Such a phenomenon is due to by lowering of the static potential accompanied with reduction of the static capacity of the photoreceptor. As a result, the developability and the image density are lowered. Particularly, problems occur in that the developability is lowered and the image density formed by the reversal development is insufficient, and a text image and photographic image having high sharpness can be obtained with difficulty only when a developer employing a small particle toner is used.
For recovering such lowering of the developability it is effective to increase the amount of charge per unit area of a thin layer organic photoreceptor so as to increase the electrical field intensity per unit layer thickness. However, both image defects of black spotting and white spotting tend to occur during reversal development when the electrical field intensity per unit thickness of the photoreceptor is raised. Namely, the image defect of black spotting tends to form since charge injection unrelated to the image is increased, in relation to the increase of the electrical field intensity in the photoreceptor. As methods to prevent such black spotting defects, countermeasures providing an interlayer and an electrical isolation layer on the surface of the conductive substrate by anodization to prevent the injection of free carriers. For example, a photoreceptor has been proposed which has a thin photoreceptor layer and an interlayer containing titanium oxide particles as disclosed in JP-A 2002-196522. However, black spotting cannot be sufficiently prevented during reversal development by the foregoing method which causes the increased electrical field intensity.
On the other hand, image sharpness tends to be degraded since an image defect, so called white spotting is formed when the electrical field intensity-is raised. It is assumed that the surface charge at the exposed areas does not disappear which is caused by filming of small toner particles. When the surface charge of the photoreceptor is increased, the ability to clean the toner is lowered due to a rise of Coulomb's force between the photoreceptor and the toner particles so that the white spotting tends to occur. The defect of white spotting easily occurs due to the increase in the surface area when extremely small particle toner is used.


A package includes a base body having a mounting portion for mounting a light-emitting device, a frame-shaped first reflection member attached to the upper surface of the base body, an inner peripheral surface of which is shaped into a first light reflecting surface and surrounds the mounting portion, and a frame-shaped second reflection member attached to the upper surface of the base body, with a spacing secured between an inner peripheral surface of the second reflection member and an outer peripheral surface of the first reflection member, the inner peripheral surface surrounding the first reflection member and having a second light reflecting surface at a location above an upper end of the first reflection member.

A light-emitting apparatus of conventional design is mainly constructed of a package for a light-emitting device (hereafter also referred to simply as a "package"), a light-emitting device, and a light-transmittable member. The package is composed of a base body and a reflection member. The reflection member is formed in the shape of a frame, the inner peripheral surface of which is shaped into a reflecting surface for reflecting the light emitted from the light-emitting device.
In this light-emitting apparatus, the light-emitting device is allowed to emit light by a driving current supplied from an external electric circuit. In recent years, such a light-emitting apparatus has come to be utilized as a light source for illumination purposes, and this trend has created a demand for a light-emitting apparatus which exhibits excellent distribution of luminous intensity and heat dissipation capability in an operating state. Moreover, in the case of using the light-emitting apparatus as a light source for illumination purposes, its service lifespan is of particular importance. Consequently, not only a brightness of higher level but also a longer lifetime has been demanded of the light-emitting apparatus.
In light of the foregoing, nowadays, research and study have been made to come up with a variety of configurations of the reflection member for attaining a stable luminous intensity distribution in the light-emitting apparatus.
Japanese Unexamined Patent Publication JP-A 10-107325 (1998) discloses a related art.
However, the above-described conventional light-emitting apparatus poses the following problems. That is, in the case of bonding a large-volume reflection member having an reflecting surface which exhibits desired reflection characteristics, the base body and the reflection member suffer from troubles such as a stress and a bending moment caused by a difference in thermal expansion coefficient, during for example, the process of package production or the operation of the light-emitting apparatus. Sometime, it causes the package an insufficient hermetic sealing.

Package for light-emitting device, light-emitting apparatus, and illuminating apparatus