Food container utilizing titanium oxide particles and method for preparing the same

0001Specification

0002A food container using titanium oxide particles, and a manufacturing method for the same Technical field

0003it is related with the food container using the present invention and titanium oxide particles -- it is detailed -- even when it becomes dirty, it enables it to wash easily again that it is hard to become dirty To et al. It is To for improvement in the mechanical strength to be also possible when a food container is a glass container. To is made and the food container which these effects maintain over a long period of time is provided. It is. Drinks, such as beer, are also included with foodstuffs here.

0004this application -- patent application to Japan (Japanese-Patent-Application-No. 1 0 -- 3 5 0 4 0 6 No. and Japanese-Patent-Application-No. 1 1 -- 2 86 1 1 4 No.) it is based -- the written contents of the Japanese application concerned -- this specification A part shall be used and it shall be taken in.

0005This application is the U.S. application number 6. 0 A 1 3 6 and 2 3 1 and (filing date :1 9 9 9 year 5 moon 2 six days) U.S. application (filing-date : January [ 1 9 9 nine year ] 2 [ 2 ] and application number undecidedness) The profits of the based application are asserted. Background art

0006The barrel, the evening which carry or store drinks, liquefied food, etc., such as beer, juice, and milk To food containers, such as An, and food containers, such as a large-sized tank used for tanker 1 car Containers, such as glass, a plastic, and metal, are used according to the use. this -- especially in inside, since endurance is excellent, metal containers are used widely -- To et al. Since it is hard to rust, the container made from stainless steel is used widely. On the other hand, it is glass. The container is found useful from fields, such as flexibility of shape, and low cost.

0007from [ the food container aiming at conveyance or storage, and that repetition use is carried out ] -- again -- A store since it is used outside in many cases, the outside, a tap, etc. of a container do not become dirty easily -- again -- Even when it becomes dirty, what can be washed easily is desired. glass container it compares with the product made from stainless steel, and since intensity is weak, it has thick structure -- weight is heavy that much. Therefore, the weight saving is called for.

0008in order to be hard to become dirty about a food container -- the surface of a container -- fluororesin -- Cau fluorine treatment, such as acting as Tyng, is carried out -- size Listen of the angle of contact with water is carried out -- namely, water-repellency There are surface treatment methods, such as the method of raising a sex.

0009however, surface place of coating the surface of a food container with fluororesin it sets to the method of carrying out Reason -- the color of the used coating agent is influence to the color of a food container In order to give, as a surface treatment method of the food container in which feeling of purity is searched for, it is not desirable. When -- there was a problem to say. moreover -- wearing Co 1 Tyng out, while using it Or it exfoliates -- there was a problem in prolonged use.

0010The case where the quality of the material of a food container is glass, in order to carry out the weight saving of the container, it is To thinly about thickness. There were To and a problem that mechanical strength fell.

0011it comes out the object of the present invention and to wash easily again that it is hard to become dirty, even when it becomes dirty It comes and such an effect is providing the food container maintained over a long period of time. Special Also when a food container is glass and thickness of glass is made thin, strength [ mechanical ] Also let it be the object to enable it to also maintain a degree. The indication of an invention

0012The food container of the present invention and titanium oxide particles are made to exist in the surface. Therefore, that it is hard to become dirty, also when it becomes dirty, it can wash easily again.

0013it differs from a resin Co 1 Tyng agent -- since the titanium oxide film is excellent in transparency, the original appearance of a container can be kept -- for example, if it is metallic containers, such as stainless steel, it can be considered as a container with feeling of purity with metallic luster. The quality of the material of a food container is glass. Since the mechanical strength can also be united and can be raised if it is a case where it is make, it is possible to consider it as a bottle with lightweight as a possible next door and a result making glass thickness thin. It is. The best form for inventing

0014Hereinafter, the present invention is explained in detail.

0015What is used for conveyance of the food container, foodstuffs, and the drink which are used by the present invention, storage, etc. If it is, there will be no restriction in particular, It is fate about drinks, liquefied food, etc., such as beer, juice, and milk. Containers, such as the bottle and barrel which carry out Carrying, and a tank, or the large-sized evening used for tanker 1 car An etc. are mentioned. in order to carry and store the quality of the material of these containers, foodstuffs, etc. -- A low if suitable in respect of the whole surface and health, there will be no restriction in particular -- usually -- glass and plus tic -- although metal etc. are used it is desirable from using it [ Or / carry ] -- metal and glass excellent in endurance are used. As a metal, it is to rust. Stake stainless steel is preferred.

0016as such a food container, it is used outdoors in many cases -- again -- especially -- tap Beer barrel made from stainless steel which becomes dirty easily and is hard to wash since it is uneven-shaped [ complicated ] Lee evening 1 Nabeul glass bottle consisting of soda lime glass, borosilicic acid glass, etc., etc. It is.

0017the titanium oxide particles used by the present invention and ultraviolet rays are used -- an organic matter etc. -- Disassemble it has a photocatalyst function which can do To -- disassembly of organic matters, such as dirt of foodstuffs origin, sterilization, and Or Effects, such as occurrence prevention of Facial expression, are produced. Since titanium oxide particles have high hydrophilicity, they can prevent adhesion of organic matters, such as an oil ingredient of foodstuffs origin, the particulates of an inorganic system, Sand dune, etc. since the mechanical strength improves when titanium oxide particles are used for glass containers, glass thickness can be made thin -- as a result, the weight saving of the whole glass container -- Connect.

0018if it is such titanium oxide particles, there will be no restriction in the crystal structure -- usually -- tetragonal phase An announcer evening [ of the low temperature type in a system ]-Ze type, a high temperature type rutile type, and bull 1 Kite type acid of an ortho rhombic system Although-izing titanium particles are used Preferably it is Including about bull 1 Kite type titanium oxide particles. The titanium oxide particles which it has are used. Titanium oxide particles including a blue kite type crystal Acid of bull 1 Kite type titanium oxide particle independence or a rutile type, or an announcer evening-Ze type -izing titanium particles may also be included. the titanium oxide particles of a rutile type or a Anatase type are included a case -- the rate of the blue kite type titanium oxide particles in titanium oxide particles -- especially -- restriction -- There, 1*1 [ usually, ] 0 it is 0 % of the weight -- desirable -- 1 0*1 0 0 % of the weight -- good Wait 5 to spread 0*1 0 It is 0 % of the weight. This and bull 1 Kite type titanium oxide is Luchi. It is because Le type announcer evening 1 Ze type titanium oxide is excelled in the photocatalyst performance. A manufacturing method of the titanium oxide particles containing a bull 1 Kite type crystal, Anatase type acid Manufacturing method in the gaseous phase which obtains the titanium oxide particles which heat-treat-izing titanium particles and include a blue kite type crystal, Titanium tetrachloride, titanium trichloride, titanium Alkoxide, and sulfuric acid Chita It is acid by neutralizing the solution of titanium compounds, such as A, or hydrolyzing. There are a manufacturing method in the liquid phase acquired as titanium oxide sol which-izing titanium particles distributed, etc. The thing containing these methods and the titanium oxide particles containing a blue kite type crystal Although there will be no restriction in particular if it is a manufacturing method obtained, The photocatalyst performance of the obtained substance, and treatment From book from the transparency at the time of forming the thin film of easy and titanium oxide, adhesion nature, and film hardness The method shown in the example of Ming is preferred. Namely, 7 5*1 0 It is a Chi tetrachloride to hot water of 0 °C. A tongue is added and it is 7. It is more than 5 °C and is the temperature below the boiling point of solution, He is Cong about chlorine ion concentration. Titanium tetrachloride is hydrolyzed, carrying out a trawl, It is a bull top chaya as oxidization Chi evening Sol. How to obtain the titanium oxide particles containing a A type crystal, 75*1 hot water of 0 O t -- 4 a titanium chloride is added -- the bottom of existence of either one of nitrate ion or phosphoric acid ion, or both sides 7 it is more than 5 °C -- temperature below the boiling point of solution, chlorine ion and nitrate ion -- and -- titanium tetrachloride is hydrolyzed, controlling the concentration of the sum total of phosphoric acid ion -- method of obtaining the titanium oxide particles which contain a bull 1 Kite type crystal as titanium oxide sol It is desirable.

0019Although there is no restriction in particular, the average particle diameter of the size of titanium oxide particles is usually 0.0. 0 It is 5* 0. if this is larger than 0 .1 z m, photocatalyst activity falls, and even when it becomes dirty, an organic matter will be disassembled easily again that it is hard to become dirty -- it can wash When -- it is because the effect to say is hard to be acquired. the transparency of titanium oxide particles falls -- the food container which made such titanium oxide particles exist in the surface -- titanium oxide particles a color affects the color of a food container -- it is not desirable. 0 .0 0 It is small from 5 w m. Handling by the process of manufacturing the time and titanium oxide particles is difficult. Oxidization Chi The specific surface area of tongue particles, usual, and 2 0 m²It is above.

0020Thus, method in which the obtained titanium oxide particles are made to exist on the surface of a food container If it carries out, the sol of titanium oxide particles is applied to a food container -- the method of making it adhere on the surface of a food container by dryness, heat treatment, sintering, etc. after that, and titanium oxide particles -- paint etc. it mixes and applies to a food container -- there are the method of drying and heat-treating after that, etc. Titanium oxide Particles may be fixed to a food container with a binder etc. as it is.

0021if p H of the sol of titanium oxide particles is less than one -- metal foodstuffs, such as stainless steel since a container may be made to corrode -- filtration washing, electric dialysis, ionic exchange, and electrolysis etc. -- it is preferred to control p H or more to one.

0022The method of applying the sol of titanium oxide particles to a food container is a spin although there is no restriction in particular. The coat method, the Flo one quart method, a dip coating method, a spray coating method, and one quart of Ba Even if it uses any of publicly known methods, such as a method, the roller coat method, a brush coating method, and the immersing method It is and is .. it is made the amount of applications in the case of applying titanium oxide sol, and the applied membranous thickness -- usually -- 0.0 1*; L 0 It is 0 m.

0023the sol of titanium oxide particles is applied to a food container -- after that -- dryness, heat treatment, sintering, etc. When making it adhere to an intermediary and the surface, it is also possible to add a sintering aid or a binder, and a binder precursor to titanium oxide sol. a food container -- oh -- rudder Because -- a binder -- 1 is applied -- ground processing which forms an undercoat layer may be performed. A sintering aid and a binder are height and film hardness about the adhesive strength of titanium oxide particles and a food container. It is made to improve. it is use about addition of such a sintering aid, or a binder titanium oxide particles become difficult to separate by carrying out from a food container -- it continues for a long period of time -- it is hard to become dirty, or even if it becomes dirty, the effect which can be washed easily continues.

0024Material of the food container which uses the kind of sintering aid or binder 1, and binder 1 precursor although it changes with quality, if it is Bremstedt acid, there will be no restriction in particular in a sintering aid -- for example, organic carboxylic acid, such as phosphoric acid, chloride, or acetic acid, etc. are used. a binder -- for example, oxidization silicon, titanium oxide, and an aluminum oxide, metal oxides, such as a zirconium dioxide, a calcium oxide, and magnesium oxide, are used -- binder precursive The Alkoxide object etc. which have the metal have adhesion and film strength raised by the body. It is desirable. Especially preferably they are phosphoric acid which is a sintering aid, and a binder precursor. The Alkoxide object of silicon, such as tetra-methoxysilane and tetra-ethoxy Silane, and Chita Titanium which is a Alkoxide object of A, acetate of titanium, and a binder is sharp, and it is 1 ♪. It is the body. alkoxy one of silicon, such as tetra-methoxysilane and tetra-ethoxy Silane a Do object is condensed and forms Pori Shiroki Sun and organopolysiloxane -- binder It becomes.

0025The surface of titanium oxide particles, In the atmosphere, it is covered with oxygen or a hydroxyl group. Phosphoric acid, oxidization silicon which builds the Syros Knoll combination, and its precursor, Or titanium oxide and That A precursor is used, A sintering aid or a binder is a food container and acid. It condenses with the surface of-izing titanium particles, respectively, In order to join together powerfully Adhesion excellent in a small quantity Power is revealed., Even if a food container is metal, a metaled oxide layer in substance and the surface Since it exists, adhesiveness with a binder is strong. the quality of the material of a container -- stainless steel a case -- a sintering aid -- phosphoric acid is used suitably. Silicon, such as tetra-methoxysilane which is binder 1 precursor when the quality of the material of a container is glass, and tetra-ethoxy Silane A Alkoxide object is used suitably.

0026Such a sintering aid, Binder, Acid formed using a binder precursor Hardness of a-izing titanium thin film, Although a material of a container is also influenced When phosphoric acid is used, it is a lead in general. Brush hardness It is more than 4 H., Oxidization silicon Zirconium dioxide Titanium oxide and them When a precursor is used, it is pencil hardness in general. It becomes more than 6 H, It excels in film strength, To peeling It becomes a stake thing.

0027Even if it uses these sintering aids and binders 1, one-sort independence, or two sorts or more It is and is .. The mixed rate can be chosen arbitrarily the case where these are mixed and used. It is 1 to the amount of addition in the case of adding a sintering aid, usual, and titanium oxide. 0 p p m* 1 0 0 0 It is 0 p p m. 1 0 0 0 if more than 0 p p m -- sintering temperature -- high -- To set up there is Need to -- sintering time is taken and it is not desirable. It is if less than l O p p m. There is no sintering effect preferably [ it is small and ]. Place which adds a binder and a binder precursor It is [ as opposed to / usually / case where the amount of addition of Synthesis and they are converted as an oxide / titanium oxide ] 5*5. It is 0 % of the weight. 5 oxidization Chi which will be buried into a binder if more than 0 % of the weight since the rate of tongue particles becomes large, the photocatalyst activity of a coat falls -- 5 % of the weight -- few -- if there is nothing, the effect of binder 1 will not be acquired -- it is not desirable.

0028Although the addition method of sintering aid or binder 1, and binder 1 precursor does not have restriction in particular, The method of applying to a food container, after adding these to titanium oxide sol, and titanium oxide When applying sol with a spray coating method, they are a sintering aid or a binder, and a binder. There are the method of applying one precursor from another spray, etc.

0029the sol of titanium oxide particles is applied to a food container -- the case where it dries after that -- Drying speed A suitable solvent may be added in order to make a degree quick. Usually, titanium oxide sol is a part to water. When scattered, organic solvents, such as ethyl alcohol, are used.

0030before applying the sol of titanium oxide particles to a food container -- titanium oxide the solution which contains silica, a fluoro-resin, etc. in order to prevent a food container deteriorating -- foodstuffs the surface of a container is covered -- it is made to dry -- a protective film may be formed.

0031Thus, it is a titanium oxide grain to the food container after applying the sol of titanium oxide particles. In order to make a child fix to the surface, dryness, heat treatment, etc. are performed. Atmosphere of dryness and heat treatment mind does not have restriction in particular -- although carried out by the inside of the atmosphere and a vacuum, and the inactive gas middle class, it is usually carried out in the atmosphere. The temperature, The quality of the material of a food container, Sintering aid, Binder, By Although it changes also with the kinds when Nda 1 precursor is used It is usually 2 0*8 0 0 °C., A sintering aid and binder, When using a binder precursor, it is 2 0 *4 5 0 °C. the time of dryness and heat treatment -- usually -- for 5 minutes -- * 2 4 hours -- desirable -- 1 for 5 minutes -- * 1 It is 2 hours.

0032For example, when the quality of the material of a food container is stainless steel or glass, As a sintering aid Phosphoric acid is used and it is 1. 0 0*4 5 It processes by 0 °C, Binder 1 and binder precursor It carries out and is tetra-methoxysilane of oxidization silicon or its precursor, using tetra-ethoxy Silane, etc. Alkoxide of titanium, Curette, acetate, etc. -- 2 0*4 5 0 °C -- place It comes out to raise more the film hardness formed by titanium oxide particles, if Reason is carried out. It comes and is desirable. this case -- the time of heat treatment -- usually -- for 5 minutes -- * 2 4 hours -- desirable -- 1 for 5 minutes -- * 1 It is 2 hours.

0033Thus, it is 2 when a sintering aid, a binder, and a binder precursor are used. 0*4 5 Since titanium oxide particles are fixable to the container surface at the low temperature 0 °C, it is heat treatment. The energy cost of a sake can be held down low. the quality of the material of a food container -- Ga glass is heated to an apparent initial softening and titanium oxide particles are made to fuse the case where he is Russ -- things Oxidization Chidan particles are fixable to the container surface at To and a temperature lower than the apparent initial softening of glass. Therefore, modification of glass can be prevented. the apparent initial softening of glass -- usually -- 5 0 0 °C -- with -- It is a top.

0034thus, the obtained titanium oxide particles are set to the food container made to exist in the surface -- the thickness of the thin film -- usually -- 0.0 0 5*1 0 m -- it is -- desirable -- 0.0 It is 3 *0 .5 m. 0 .0 0 If photocatalyst activity and hydrophilicity are enough when thinner than 5 m There is nothing. 1 if thicker than 0 i m -- a photocatalytic reaction -- near the surface of a titanium oxide thin film -- Done it is that of To be -- the titanium oxide which does not participate in a photocatalytic reaction will increase in number, and economically advantageous it is not -- it carries out -- a thin film exfoliates easily from a food container. Transparent of a titanium oxide thin film Mind falls -- it is not desirable.

0035thus, the food container which made titanium oxide particles exist in the surface and titanium oxide particles dirt adhering by the photocatalyst function is disassembled -- the microorganism which contacts can be killed and wounded again or the multiplication can be suppressed. titanium oxide particles are excellent in hydrophilicity -- the water an angle of contact -- 2 since it was 0 times or less, it stuck to the food container -- it becomes dirty -- for example, the outdoors Are hard to attach the dirt of the outside of the container at the time of using it, the dirt of a tap, etc., or they become dirty. It can wash easily also by a It was case. moreover Are formed of titanium oxide particles. It was film, It excels in transparency. A color of a food container is not affected. A food container is Gala. In being a container made from A, the mechanical strength also improves by a titanium oxide thin film. A binder and/or a sintering aid are used for titanium oxide particles, and it is the surface. It is made to exist, titanium oxide particles paste the food container surface powerfully -- film it excels in hardness -- it is hard to separate -- the above-mentioned effect by titanium oxide particles -- long period of time It crosses and continues. They are titanium oxide particles to the surface of a food container in this case. The temperature made to fix is 2. 0*4 5 Since it is the low temperature 0 °C, it is A for heat treatment. While being able to hold down Energy cost low, The quality of the material of a food container is glass. Modification according to the heat in a case can be prevented.

0036it is used also on such a food container, and not only indoor but the outdoors -- again -- especially -- Note Squirrel which was the shape which has curvature with size complicated in Spout being uneven-shaped [ complicated ] To sake, To the beer barrel made from stainless steel which becomes dirty easily and is hard to wash, and glass beer bottles It is applied preferably. As for the ingredient of beer, water is 9. 1*9 3 % of the weight and ethanol are 3.3*3.9 % of the weight, an extract -- 3. : !. * 4 .0 % of the weight and carbon dioxide -- 0.4 2*0.5 it is 5 % -- all the sugar, such as an extract which is a nonvolatile organic in this, and dextrin from -- the becoming carbohydrate -- 7 5*8 It contains 0% of the weight. Therefore, inside of a beer ingredient Especially an extract serves as a proximate cause of dirt.

0037The dirt by organic matters, such as such dextrin, is Including about a blue kite type crystal etc. It is decomposed by the photocatalyst function of the titanium oxide particles which it has, and is hard to become dirty, or becomes dirty. It can wash easily also by a It was case. EXAMPLE

0038Hereinafter, an example is given and the present invention is explained concretely.

0039Example 1

0040Distilled water 954mL is inserted in the glass reaction vessel of content volume 1 L with a reflux condenser, and it is 9.

00415 It warmed to °C. next, a reaction vessel is agitated by abbreviation 200 r pm -- boiling the solution temperature in a tub by 95 while maintaining -- titanium tetrachloride solution 46mL -- the speed of abbreviation 2mLZm i n -- reaction vessel It was dropped. Thus, titanium tetrachloride concentration is 0. 25mo l ZL (2 % of the weight of oxidization Chita A conversion). Solution was obtained. it heats to the end back of dropping, and near boiling point (104degreeC) -- it held for 60 minutes at the temperature, and hydrolyzed titanium tetrachloride. it is cooling about the obtained sol it condenses -- the chlorine generated by hydrolysis -- Asahi Chemical Industry Co., Ltd. -- make apparatus-for-electrodialysis G 3 type -- business it is and removes by electric dialysis -- water of pH=4. 0 (chlorine ion about 400 p pm) Distributed titanium oxide sol was obtained. the particles in sol were observed with the transmission electron microscope time -- particles -- particle diameter was 0. 01*0. 03 m.

0042It is this sol in order to investigate the crystal structure of the titanium oxide particles contained in this sol.

0043it is made to dry with the vacuum-drying machine of 60 degreeC -- obtained titanium oxide particles Analyze by an X diffraction. It was. An X diffraction is Rigaku. Make X diffraction Device (RAD -- B rotor Fleck A) performed, and the bulb used Cu. As a result, bull 1 Khai ♪ type crystal (121) The peak which shows diffraction of a field was detected by 20 = 30.8 ". A rutile type and the announcer evening -- The Ze type was not detected.

0044Water distribution titanium oxide sol containing the bull 1 Kite type titanium oxide obtained as mentioned above Tetrameth which is silicon system adhesives as a binder precursor in order to apply Ethyl alcohol for raising Xylosilane and a drying rate was added, and the paint of the composition shown in Table 1 was prepared.

0045the obtained paint -- beer barrel made from stainless steel (capacity 10L) it applies by a brush coating method -- it heat-treats by 1-hour dryness back, inside of the atmosphere, and 200"C by 50 degreeC among the atmosphere for 2 hours -- the beer barrel which made the titanium oxide thin film of film thickness 0. 4 z m exist in the surface was obtained.

0046Thus, it is a spray about beer 1 L to the upper surface and the side on the surface of a beer barrel which were acquired. Viewing estimated the appearance of the neglect back and this beer barrel for three months to spraying and the outdoors with the vessel. the portion of dirt of the complicated uneven shape of a tap is especially strong -- this portion -- criticism of the difficulty of becoming dirty Value was carried out. then, water temperature 2 Shower water 1 of 0 °C 0 L is showered over a beer barrel -- becoming dirty Viewing estimated the ease of washing. the result -- a table -- it is shown in 2.

0047Table 1

0048<img file="WO0034146A1_D0001.tif" />

0049Table 2

0050Example number The difficulty of becoming dirty The washing ease of carrying out

0051Example 1 O O

0052Example 2 O O

0053Example 3 O O'

0054Example 4 O O

0055Example 5 O O

0056Example 6 O O

0057Comparative example 1 X X

0058The cable address in comparative example 2 X X table 2 shows the following contents, respectively.

0059(1) The difficulty of becoming dirty

0060O It is hardly dirty.

0061O It is Dirty Youth 1000.

0062It became in X and is dirty.

0063(2) The ease of washing

0064O Dirt comes off immediately.

0065O Dirt Cannot Come Off a Little Easily.

0066X dirt does not come off.

0067Example 2

0068It is phosphoric acid before titanium tetrachloride solution is dropped P0₄³as -- 200 p pm To -- it is made to be the same as that of Example 1 except having added to the reaction vessel like -- titanium tetrachloride -- an added water part It understood. Water distribution titanium oxide sol is obtained like Example 1 except having set pH of the obtained sol to 1.9 (chlorine ion abbreviation 600 p pm, phosphoric acid ion about 2 O O p pm). It was. When the particles in sol were observed like Example 1, the particle diameter of particles was 0. 01*0. 03 m.

0069The crystal structure of the titanium oxide particles contained in this sol is investigated like Example 1. It was. As a result, bull 1 Kite type crystal (121) The peak which shows diffraction of a field, and rutile The peak which shows diffraction of (1 10) side which is a main peak of type was detected. Since it overlaps with the main peak of an announcer evening-Ze type main peak and a blue kite type, it is a seal. Although an exception was not able to do, the peak which shows diffraction of (004) side of an announcer evening 1 Ze type crystal detects. It was carried out. Therefore, the obtained sol was a mixture of the blue kite type crystal, the announcer evening-Ze type crystal, and the rutile type crystal. The content of these crystals is computed as follows. It carried out.

0070titanium oxide of a blue kite type crystal, an announcer evening 1 Ze type crystal, and a rutile type crystal -- it -- a Re table -- it is shown in 3 (J CPDS card extract) although it has an X diffraction peak -- these -- That There are many portions overlapping so that d value may show. especially d values of a Ze [ The bull 1 Khai ♪ type and the announcer evening - ] type main peak are 3.51 and 3.52, respectively -- it carries out -- further -- The the Lou Kite type has a peak also in 3.47 -- these 3 person's peak -- substantial -- umbrella It becomes.

0071thus, the intensity ratio of the main peak of a bull 1 Kite type and an announcer evening 1 Ze type -- eye Request -- , -- Since there is no Re Blue kite type which does not overlap with an announcer evening 1 Ze type peak here (1 2 1) The peak of a field is used, it asks for intensity ratio (peak intensity of A blur 1 Kite type (12 1) side)/(peak intensity with which three persons overlap) of the peak to which the three above-mentioned persons' peak overlaps with this -- from now on, it asked for the content of titanium oxide of a bull 1 Kite type and a Anatase type. Peak which shows diffraction of (1 10) side which is the main peak about a rutile type Intensity ratio of the peak with which the three above-mentioned persons overlap (rutile type main peak intensity) It asked for content from Z (three persons overlapping peak intensity).

0072As a result (blue kite type (121) peak intensity of a field), it is Z = (A with which three persons overlap -- The intensity) 0.38 (rutile type main peak intensity), and Z (peak intensity with which three persons overlap) = 0.05, a bull 1 Kite type crystal -- 70 % of the weight of abbreviation, and rutile type crystal as for 28.8 % of the weight of abbreviation, the announcer evening 1 Ze type crystal is included about 1.2% of the weight -- I The One † second.

0073Water distribution oxidization Chi containing the bull 1 Kite type titanium oxide containing phosphoric acid obtained as mentioned above Ethyl alcohol for raising a drying rate to tongue sol was added, and the paint of the composition shown in Table 1 was prepared.

0074thus -- making it be the same as that of Example 1 except having used the obtained paint -- oxidization Chita the peel barrel which made A particles exist in the surface is obtained -- it evaluated similarly. the result -- a table -- it is shown in 2. Table 3

0075Brookite (29-1360) Anatase (21-1272) Rutile (21-1276) d value Crystal face Intensity ratio d value Crystal face intensity ratio d value crystal face Intensity ratio

00763. 51 120 100 3. 52 101 100 3. 25 1 10 100

00772. 90 12 1 90 1. 89 200 35 1. 69 221 60

00783. 47 1 1 1 80 2.38 004 20 2.49 101 50 Example 3

0079Water distribution titanium oxide sol which consists of an announcer evening-Ze type crystal which does not contain a blue kite type

0080(Specific surface area abbreviation 2 7 0 m)²Z Be with silicon system adhesives as a binder precursor to g. It is Attach about ethyl alcohol for raising a certain tetra-methoxysilane and drying rate. Addition was carried out and the paint of the composition shown in Table 1 was prepared.

0081thus -- making it be the same as that of Example 1 except having used the obtained paint -- oxidization Chita the beer barrel which made A particles exist in the surface is obtained -- it evaluated similarly. the result -- a table -- 2 It is shown. Example 4

0082Water distribution titanium oxide sol which consists of a rutile type crystal which does not contain a blue kite type (ratio surface area 5 0 m)²Thet who is silicon system adhesives as a binder precursor at /g lame -- a crested ibis -- ethyl alcohol for raising Sicilan and a drying rate was added, and the paint of the composition shown in Table 1 was prepared.

0083thus -- making it be the same as that of Example 1 except having used the obtained paint -- oxidization Chita the beer barrel which made A particles exist in the surface is obtained -- it evaluated similarly. the result -- a table -- 2 It is shown. Example 5

0084Instead of the beer barrel made from stainless steel, it is a glass beer bottle. (large bottlet: 5 3 5 m l) Glass beads which recognized surface existence of the titanium oxide particles like Example 1 except having used One Le bottle was obtained and it evaluated similarly. the result -- a table -- it is shown in 2.

0085The strength test was carried out about this glass beer bottle. Intensity measurement is simple. The glass and the glass board of 5 c m x 5 c m x 1 .2 m m of the ingredient which constitute a beer bottle as a measuring method were used as substitution. this glass board is placed on a smooth stand -- the upper part , -- diameter 1 Free fall of the stainless steel bead of 0 mm was carried out. under the present circumstances, free in a stainless steel bead the height to drop is raised gradually -- a glass board -- cracking (divide) It is measurement about the height which enters. it carries out -- it was considered as destructive generating height. the result -- a table -- it is shown in 4. Mechanical strength, so that height is high Excelling is shown. Measurement showed the 5 times deed and the peak price of them. Table 4

0086<img file="WO0034146A1_D0002.tif" />

0087Example 6

0088Instead of the beer barrel made from stainless steel, it is a glass beer bottle. (large bottlet: 5 3 5 m l) Glass beads which recognized surface existence of the titanium oxide particles like Example 2 except having used One Le bottle was obtained and it evaluated similarly. the result -- a table -- it is shown in 2.

0089A strength test is carried out like Example 5 about this glass beer bottle. It carried out. the result -- a table -- it is shown in 4. Comparative example 1

0090Unsettled beer barrel made from stainless steel (capacity 1 0 L) which does not make titanium oxide particles exist in the surface was similarly estimated as Example 1. the result -- a table -- it is shown in 2. Comparative example 2

0091Unsettled glass beer bottle (large bottlet: 5 3 5 m l) which does not make titanium oxide particles exist in the surface was similarly estimated as Example 1. the result -- a table -- it is shown in 2. This The strength test was carried out like Example 5 about glass beer bottles. the Result -- a table -- it is shown in 4.

0092They were the beer barrel which made titanium oxide particles exist in the surface as shown in Table 2, a beer bottle, and a thing which is easy to wash again that it is hard to become dirty even if it becomes dirty. In particular, it is a blue kite type. Such [ the beer barrel which made the titanium oxide particles containing many crystals exist in the surface ] an effect Result was more excellent. the case of a bottle -- a table -- it is shown in 4 -- as -- the mechanical strength -- improvement It was carrying out. Industrial applicability

0093As for the food container of like and the present invention explained above, titanium oxide particles exist in the surface. What can be easily washed again that it is that of To and is hard to become dirty also when it becomes dirty To. What titanium oxide particles shall contain a bull 1 Kite type crystal for Therefore, the above-mentioned effect should be excelled more. .

0094it differs from a resin Co 1 Tyng agent -- since the titanium oxide film is excellent in transparency, the original appearance of a container can be kept -- for example, if it is metallic containers, such as stainless steel, it can be considered as a container with feeling of purity with metallic luster. The quality of the material of a food container is glass. Since the mechanical strength can also be united and can be raised if it is a case where it is make, it is possible to consider it as a bottle with lightweight as a possible next door and a result making glass thickness thin. It is.

0095in order to stick titanium oxide particles on a food container -- a sintering aid or by since The can be used, oxidization Chi evening A particles do not separate easily -- what can be washed easily [ also when it becomes dirty again ] that it is hard to become dirty over a long period of time It becomes. It is 5 when a sintering aid or a binder is used. 0 High temperature more than 0 °C Titanium oxide particles can be fixed to the food container surface, without heat-treating.