TW442429B - Container for high purity liquid chemicals - Google Patents

Abstract

A container does not cause any quality deterioration of high purity chemicals (4) included therein during the storage and transportation thereof and is not easily broken. The container also permits easy and safe discharge of the high purity chemical. The container for a high purity chemical comprises a flexible internal container (2) formed from a polyolefinic high purity resin and a gas-tight, self-supporting external container (3), which accommodates the internal container, wherein these internal and external containers are joined together in such a manner that the space formed between these two containers are arbitrary closed and opened so as to ensure the communication with the outside, a liquid-discharge pipe (16) provided with a check valve (19) connected to the pipe midway therein is gas-tightly inserted into the internal container down to the bottom thereof and a connector (12) connected to a pressure source (11) is fitted to the external container.

Description

* 442429

-The present invention relates to a container for storage and discharge of a high-purity chemical liquid used in the field of semiconductors and liquid crystals. [Previous technology] In recent years, due to the rapid progress of electronic components, the design process rules of integrated circuits have also become a trend of miniaturization. As mentioned above, the high-purity medicinal solution such as the photoresist solution used in the microfabrication process is required to be stored and transported. It cannot be caused by the increase of impurities, the deterioration of components, and the composition. Change, impure metal elements increase, or the light of the light-sensitive components leads to the phenomenon of quality degradation—generating ° is mainly because the material of the container is dissolved and immersed in the photoresist solution, so that there will be impurities in the photoresist solution. The increase and the deterioration of the components occur. When the deteriorated photoresist liquid is coated on the substrate to form a photoresist film, pinholes will occur. In addition, the organic solvent penetrates into the high-purity chemical liquid, which causes a change in the composition of the high-purity chemical liquid. At this time, since the viscosity of the photoresist liquid is changed ', the thickness of the photoresist film is changed. The reduction in the quality of these photoresists will bring the quality and success of semiconductors and liquid crystal displays.

The effect of "00 rate" is quite bad. As a result, the shelf life of the photoresist liquid J, the so-called cleanliness, is used as an indicator showing that the photoresist liquid is stored in the photoresist liquid for a long time. During the period of the container, impurities are dissolved and leached, so that the quality is reduced. After storing the ultrapure water or photoresist solution in the test container for a short period of time, calculate the storage in the store

A42A 2 9 V. Description of the invention (2): The number of particles with a particle size of 0 2 _ or more in the content of 1 ml of the liquid 9 ′ in order to obtain the cleanliness. It is said that the knowledge of 1 technician defines the percentage of 屮 4 4 4 Λ Ju more specifically by the following formula, and the so-called cleanliness. [Formula 1] Cleanliness (pieces / m 1) = c (pieces) xa / 2 (ml) (1) b (ml) Xa (ml) * In formula 'a is the capacity f of the inspection container, In addition, b is the amount of content liquid sampled from the inspection container. First of all, take the inspection step '^ as the "measurement of the initial cleanliness; the amount of aW in the inspection container, put a / 2 (ml) in each photoresist solution'" and shake it for 15 seconds, In addition, the sample solution β, which was taken for 24 hours to stand, was stored in a container for a certain period of time after being subjected to the initial cleanliness measurement treatment, and was left in a state where no air bubbles occurred. And after rotating the container 3 times, the sample & which is used to measure the so-called content after storage is taken. The material # is calculated from the total amount of the so-called sample solution by a micro-counter. The value of the above particles 0 is based on the aforementioned values, and the formula Π) is used to calculate the initial cleanliness and the cleanliness after a certain period of storage. The lower the cleanliness value, it indicates the photoresist solution. The better the quality. When the cleanliness is less than 1000 / m 1, the quality and yield of the semiconductor and liquid crystal display (LCD) will not be reduced. Therefore, it can be stored relatively stably. High-purity chemical liquid. • 4424 2 9 V. Description of the invention (3) Generally, a glass container or a metal container is used as a container for containing the photoresist and its surrounding medicinal solution. However, it is said that sodium ions will be dissolved by the glass container and dissolved by the metal container. Metal ions such as iron, etc. As a method for preventing such adverse effects as described above, "Japanese Patent Publication No. 6-99000" proposes a method described below: the use of an inert resistant material The container made of corrosive plastic film (polytetraethylene) and the outer bottle or multi-layer packaging surrounding the pouch are distributed by means of a dispensing device to facilitate the discharge of the high contents of the pouch. Purity drug solution. [Problems to be solved by the invention] However, the cleanliness of polytetragasethylene sachets is not in a good degree. The polytetragasethylene sachets are discarded after use, and there is a so-called use The problem of subsequent disposal is quite difficult. Moreover, polytetraethylene is relatively expensive. The present invention is completed to solve the aforementioned problems; the object of the present invention It is to provide a container that does not cause the quality of the high-purity chemical liquid to be reduced and is not easily damaged during the storage and transportation of high-purity chemical liquid such as photoresist liquid. In addition, the present invention provides a container which can It is relatively easy and safe to take out a container of a high-purity chemical liquid. [Means for Solving the Problem] The present invention completed in order to achieve the aforementioned object is as described below with reference to the so-called drawings corresponding to the embodiments. Say 'The container for high-purity pharmaceutical liquids to which the present invention is applicable is as shown in FIG. 1' The mold molded from a polyolefin-based high-purity resin

4 4242 9 V. Description of the invention (4) The flexible inner container 2 and the airtight and independent outer container 3 for storing the aforementioned inner container 2 are connected to the contents freely and openly to the outside The space between the container and the outer container, and the liquid discharge pipe 16 connected with the check valve 19 in the middle is inserted into the bottom of the inner container 2 and the inner container 2 is hermetically sealed. The outer container 3 is provided with a connector 丨 2 connected to the pressurizing source 11. As shown in FIG. 3, a container for a high-purity chemical liquid is located at the mouth portion 20 of the inner container and is used to hold the aforementioned liquid-exhausting tube μ. The air-tight holder 17 ′ is preferably screwed. On the mouth portion 21 of the outer container, it is preferable to open and close the screwing of the airtight holder 17 so that the inside of the outer container 3 can be closed and opened to the outside freely. action. In addition, the 'high-purity drug liquid container is as shown in FIG. 3 and FIG. 4', and the symptoms are sufficient to separate the upper part 16A of the liquid discharge pipe 16 connected to the check valve 19 in the middle and the content inserted into the contents. The lower part 1 6 B of the container 2 and the liquid discharge pipe 16 may further include an opening and closing cover 3 1 ′, and the opening and closing cover 31 ′ is connected to the liquid discharge pipe only for holding the liquid. The aforementioned airtight retainer 17 of the upper portion 16A is screwed onto the mouth portion 21 of the outer container interchangeably so that the inside of the outer container 3 and the inside of the inner container 2 perform the aforementioned Closed and open action. The liquid discharge pipe 16 and the airtight holder 17 and / or the opening / closing cover 31 'are preferably formed of a polyolefin-based high-purity resin having the same quality as the inner container 2. With a material like the one mentioned above, it is convenient for this high-purity medicine. The container for oral fluids ’can also prevent particles 纯度 from coming into contact with the pure drug solution 4.

88118465.ptd Page 7 442 ^ 2 9 V. Description of the invention (5) Dissolution of metal ions occurs. Polyfluorene-based high-purity resins can be used, for example, ethylene, acrylic, olefin-1, 4-methyl-pentene-1, hexene, or octene-1 olefin copolymers, and ethylene and Copolymers of olefins other than ethylene, or hybrid polymers of the aforementioned polymers. & Appropriate content of α-olefin units in the copolymer is 15% by weight or less, and the molecular structure of the copolymer is preferably atactic, isotactic, or ectopic (syndiotactic) As for the polymerization law, a low pressure method or a medium pressure method is preferred. The content of the polymer having a weight-average molecular weight of 1 XI 03 or less determined by gel permeation chromatography (GPC: ge1-permeation-chroraatography) in a polysmoke-based high-purity resin composition is Less than 5% by weight. In the container formed by using a polyolefin-based high-purity resin composition having a polymer content of 5% by weight or more, the impure particles are relatively easily dissolved into the high-purity drug solution, thereby making the high-purity drug solution The degree of cleanliness is 100 pieces / m 1 or more, so it is not ideal. Resin particles are dissolved in a solvent (o-dichlorobenzene) to form a sample solution, so that the molecular weight and molecular weight distribution can be measured by gel permeation chromatography (GPC). The determination process. The weight average molecular weight and average molecular weight were calculated by the following formulas. [Formula 2] 1 ^ 88118465.ptd Page 8 4 424 2 9

V. Description of Invention (6)

Weight average molecular weight = [Formula 3] Σ w average molecular weight =---(3) Σ (w X Μ) However, M is a molecular weight, and w is a weight percentage. As for the measurement conditions of gel permeation chromatography (GPC), after the device, it is (the name of the device, manufactured by Waters), and the column system is TSK "丨 gMH _HT (product name, Japan TOSOH (Manufactured by Tosoh) Co., Ltd., the solvent is o-digas benzene, the temperature is 丨 38 t, and the detector is a differential refractometer. When the aforementioned raw materials are polymerized to become a polyolefin-based high-purity resin A suitable amount of catalyst is used. At this time, a neutralizing agent, an oxidation inhibitor, and a light stabilizer are added to meet the needs. However, when these neutralizers and oxidation inhibitors are used, When the amount of the light stabilizer and the light stabilizer is relatively large, the neutralizer, the oxidation inhibitor, and the light stabilizer may be dissolved from the inner container 2 into the high-purity drug liquid 4, and become impure particles at medium pressure. In the state of the law, it is not necessary to add a neutralizing agent, but in the state of the lambda low pressure method, use the φ law 丨 ", for example, you use Ninghe agent as an air trap. In the Zhonghezhai system, examples include calcium, osmium, and saccharin phase a «^., Stearates of alkaline earth metals such as magnesium and barium, but they are used to improve the activity of catalysts in so-called polymerization operations. In operation, it must have a minimum of +, an α-heavier alkaline earth gold such as calcium, magnesium, and barium 4424 2 q 5. Description of the invention (7) Among the stearates And agent. When the content of the neutralizing agent relative to the resin composition exceeds 0.01% by weight, when the purity of the high-purity chemical liquid exceeds 100 pieces / ml, the quality of the semiconductor or LCD (liquid crystal display) and the Yield becomes worse. Therefore, the content of the neutralizing agent with respect to the resin composition is 0.01% by weight {or less. Examples of the anti-emulsifier system include butyryltoluene, pentaerythritol-tetrakis [3__ (3,5-di-t-butyl-4 -hydroxyphenyl) propionate], and octadecyl__3_ (3, 5 -Di-t-butyl-4-hydroxyphenyl) propionate is a phenolic oxidation inhibitor. For the same reason as the neutralizing agent, the content of the oxidation inhibitor to the resin composition is 0.01% by weight or less. Examples of the light-resistant stabilizer include 2- (fluorenyl-2-hydroxy ^ phenyl) benzyl φ and 2- (3-butylbutyl-5-methyl-2-phenyl) -5 monobenzene Phenyl azide is a light stabilizer, (2 2, 6 β —methyl-4-hexaazaridine) sebacate and poly [丨 6_ (1133'_tetramethyl $ butyl) ) Amino-1,3,5-triazine, -2,4-diylfluorene (2,2'6'6-tetramethyl ^ -4-hexahydropyridine) imino} cyclohexane {(2 , 2,6,6-tetramethyl ~ 4_ 丄 ^ bite) imine}} amine blocker is a light stabilizer. For the same reason as ^, the content of the light-resistant stabilizer with respect to the resin composition is 0.01 to 96 weight. The material with the gluten repellent device 2 is just taken from the acupoints. The properties are: ketones such as methyl ethyl ketone, etc. in the photoresist solution, esters such as methyl lactic acid, and acetic acid such as ethyl acetate and ethyl acetate. Cellulose such as vinegar cellosolve. ~ D The container for the high-purity pharmaceutical liquid of the present invention is a photoresist system for a process or a liquid crystal display, a resist solution for a conductor, and a solvent for dilution.

$ 'Excessive explanation (8) is a pure drug. As an example of a photoresist for a semiconductor process, the photoresist is an essential photoresist containing the following components: cresol novolac novolac resin, poly (vinylphenol), alkali soluble resin, benzene: Diazide-based sensitizers such as diazide sulfonate, naphthoquinonediazide sulfonate, benzoquinone di "azinesulfonamide, and naphthoquinonediazidesulfonamide. Examples of the color resist used for the liquid crystal display include photopolymerization composed of an acrylate monomer, a trifunctional methyltrigonol photopolymerization initiator, and an acrylic acid / acrylic acid copolymer. Substance, dispersed with organic pigments. Since such a photoresist contains a light component having a wavelength of 2000 to 500 nm, which is easily light-sensitive, the outer container 3 must have a so-called light-shielding property. In addition, since the outer container 3 is not in direct contact with the medicinal solution, 'if it is a material that can withstand a maximum pressure of 3.0 kg / cm2', it is not necessary to use a special material as the outer container 3 Material. The material of the outer container 3 is preferably a metal material such as stainless steel, a plastic material such as polycarbonate, polyethylene, and polypropylene. [Embodiment of the invention] Hereinafter, an embodiment of the container for a high-purity chemical liquid of the present invention will be described in detail with reference to the drawings. · The overall appearance of the container for a high-purity pharmaceutical solution, as shown in J 1 in FIG. 1, is composed of a soft inner container 2 and an air-tight independent outer container 3 for storing the aforementioned inner container 2. consist of. The inner container 2 is composed of a thin smoke-based high-purity resin film. As shown in FIG. 2, the inner container 2 is fixed on the periphery of the overlapping film.

4424 2 9 V. Description of the invention (9) The bag-shaped body having the welding portion 6 is provided, and the inner container 2 of the bag-shaped body can be broken before it is used. It is possible to blow in the clean air which has been filtered and processed through a filter, and at the same time, it is formed into a cylindrical shape by an expansion treatment so as to obtain the resin film having the inner container 2. On the tubular film of the sheet, the hole portion is opened, and the tubular bracket 29 is fused by heat sealing treatment. An unprocessed tubular film is superimposed on the tubular film ', and four sides of the tubular film are heat-sealed to obtain an inner container 2. Therefore, the inner container 2 becomes a double-layered resin film. In addition, when a multilayer structure made of a metal material such as aluminum or a plastic material such as polyamine, polyvinyl alcohol, poly (ethylene-co-vinyl alcohol) is freely selected, the inner container 2 is covered. At the outer side, the inner container 2 can be provided with light-shielding and π-blocking properties, and even safety against leakage. The tubular bracket 29 'attached to the contents is provided with a mouth portion 20, and a notch 22 is also formed. ^ As shown in FIG. 3, 'the inner container 2' is inserted with the liquid discharge S16 until the bottom, and the external body 1 discharge pipe 16 is connected to the upper part of the check valve 19 on the way UA It is composed of the lower part 16β and, on the way, the liquid discharge pipe 16 is closed and connected by the middle plug 25. The lower part 16B is closed to the mouth portion 20 of the inner container 2 and is inserted into the mouth portion 20 of the inner container 2 and the upper portion 16A is on the way, and is connected to the check valve 19, and is also fixed by The upper part 16A is fixed to the bracket 28. An appropriate number of vent holes 36 are provided in the front end portion 'of the upper portion of the liquid discharge pipe 16. 881 \ 8465.ptd Page 12

44242 9 V. Description of the invention (ίο) The two containers 3 ~ f are screwed with an airtight holding: cattle 17 'at the mouth portion 21 of the outer container 3, and the inner container 2 is closed and sealed. The airtight retainer mouth is made up of 4 male keys with a key code of 24, and a bag-shaped nut, f-shaped bracket 29, a 4-position convex key code of 23, and a concave key mark of 24, which are fitted together. At: "1" at the mouth portion 21 of the outer container 3, the k-shaped nut 26 is locked by a screw »The bag-shaped nut 26 is further provided with a vent hole 30, and the vent hole 30, When the bag nut 26 is relaxed, the space between the inner container 2 and the outer container 3 is opened to the outside world. In addition, the external container 3 'is connected to an additive source 11 of an inert gas cylindrical high-pressure bottle. The connector 1 2 ′ connected to the source for pressure by a pressure-resistant hose is provided with the following components: Ventilation holes 1 4 are used to open the residual pressure inside the outer container 3 And, the connector cover 13 'is used to block the aforementioned ventilation hole 14; and' The connector 12 is connected to the stopper 15 passing through the inside of the container 3 outside the aforementioned. A handle 7 is attached to the outer container 3 '. The outer container 3 is provided with a screw lock cover 31, and the screw lock cover 31 'is used for exchanging the airtight holder 17. The β upper cover 31 is provided with a proper number of ventilation holes 35 and gaskets 32, 33, 34. Hereinafter, the order of using the container for a high-purity chemical liquid is explained. The inner container 2 in which the lower portion 16B of the liquid discharge pipe is inserted is bent into a relatively thin state, inserted into the outer container 3, and the tubular bracket 2 9 'of the inner container 2 is filled into the mouth of the outer container 3. 2 1 in. Is to start the high-purity drug solution ’from the nozzle for drug solution introduction (not shown in the figure).

Hi 8Sll8465.ptd Page 13

44242 9 V. Description of the invention (π) The lower part of the discharge pipe 16B is injected into the text, β Π coupler Z. If there is adequate space left in the inner passenger 5§2 and the outer container 3, the injection will be stopped and the lid 31 will be closed with μL ^ ^ * * The screw is screwed to the mouth portion 21 of the outer container 3 so as to seal the inner container 2 and the lower portion ιβΒ of the liquid discharge pipe. In the state as described above, the high-purity chemical liquid is stored and rotated. : During storage and transportation-due to temperature rise, vibration, and other high-purity drug liquids, and the internal pressure of the high-purity drug liquid container also rises] b, when the lid 31 is loosened, it is as shown in the arrow of Figure 4 The "internal pressure of the outer container 3" shown by No. b passes through the cutout 22, the gasket 32, and the outer container 3, and is opened to the outside through the ventilation hole 35. The internal pressure of the inner container 2 °, as shown by the arrow c of ®4, passes between the gasket 33 and the liquid discharge pipe 16B, the ventilation hole 36, the gasket 32 and the outer container 3, The ventilation hole 35 is opened to the outside. The internal pressure of the lower part kb of the liquid tank discharge pipe, as shown by the arrow d in circle 4, passes between the liner 34, between the liner 32 and the outer container 3, and through the vent hole 3 5 Open to the outside. By performing the operation as described above, no blow-out of the high-purity drug solution 4 or blow-off of the lid 31 occurs, and the residual pressure can be released, and the lid 31 can be safely removed. When a high-purity chemical liquid is taken out from a container for a high-purity chemical liquid, as described above, "the cap 3 is loosened and removed, and the airtight holder 17 is attached to the mouth portion 21 of the outer container" so that The upper portion 16A of the liquid discharge pipe is connected to the lower portion 16B of the liquid discharge pipe. When the male key code 23 and the female key code 24 are fitted together to lock the bag nut 26 to the mouth portion 21 of the outer container, the inner container and the outer container are hermetically closed. Then when that connection

88118465.ptd Page 14 4424 2 9 V. Description of the invention (12) The connector 12 on the air pressure reducing bottle 11 is connected to the plug 15 and the vent hole 1 is hermetically closed by the connector cover 1 3 ' 4. When the regulator of the air compression high-pressure bottle 11 is opened and the air is supplied, the compressed air is introduced between the outer container 3 and the inner container 2 so that the high purity can be achieved by the inner container 2 ′ by pressure. The chemical liquid 4 ′ passes through the check valve 19 and the liquid discharge pipe 16 ′ in order to discharge the high-purity chemical liquid 4. After the air supply is stopped, when the connector cover 13 is pulled up, the ventilation hole η is exposed to facilitate the opening of the residual pressure between the inner container 2 and the outer container 3. Even if the bag nut 26 is not loosened as described above, as indicated by the arrow a (see FIG. 3), the so-called residual pressure passes between the cutout 22, the outer container 3 and the middle bolt 25. The ventilation hole 30 is automatically opened to the outside. At the same time, the residual pressure in the inner container 2 and the liquid discharge pipe 16 is also opened. Therefore, 'the high-purity chemical liquid 4 is not blown out, and' the phenomenon that the components mounted on the mouth portions of the outer container 3 and the inner container 2 are not blown off occurs. Just as described above, “Because the high-purity chemical liquid 4 in the inner container 2 does not directly contact the gas supplied from the pressurizing source 11, no gas will be dissolved in the high-purity chemical. In the liquid 4, the phenomenon of quality degradation occurs, and as a result, the so-called gas does not necessarily need to be an inert gas. Hereinafter, examples of the containers for high-purity chemical liquids in which Examples 1 and 2 of the present invention are tried, and the containers of Comparative Examples 1 and 2 other than the present invention are described. (Example 1)

88118465.ptd p. 15 f 44242 9

The resin raw material of the inner container 2 is a polymer containing a density of 2.57% by weight, 0.93 5g / cm, a melting index of 0.20 g / min, and a weight average molecular weight of 1 X 1 03 or less. And, the high-density polyethylene particles containing a neutralizing agent oxidation preventing agent and a light stabilizer are used. The expansion molding machine is used, and the aforementioned resin raw material is melted in an extruder (screw diameter: 50m / m, [/ D = 26 (D · screw diameter, l: effective screw length)), and 'From a ring-shaped mold (mold diameter: 50m, mold gap: 2.0m / m), the resin raw material is extruded and subjected to a blow molding ratio of 3.5, in order to obtain a thickness of 60 to m and cylindrical film with a bending diameter of 280min. Overlay two of the aforementioned cylindrical films, and cut the 5 Xuanqi-shaped binding film to a certain length, and at a certain part of a unilateral film in the cut binding film When the hole is opened, 'on the hole' is heat-sealed through the tubular bracket 29 'with the mouth portion 20 of the inner container' in order to fix the tubular bracket 29. Then, "the two sides of the film are overlapped, and the four sides of the film are heat-sealed" to facilitate the production of the inner container A. First, determine the cleanliness of the inner container A made in this trial. This inner container A is installed in a container other than steel (content: 4 liters). In the aforementioned container, it is manufactured by placing 2,0 liters of ultra-pure water manufacturing equipment (trade name: TORAYPURE LV-1 0T (TORAY d Co., Ltd.)). Ultra-pure water, and attach the screw cap to 'close the container tightly, and perform vibration for 5 seconds, and at the same time, after standing for 24 hours,' take 5 mi of ultra-pure water to facilitate the use of a particle counter ( Model: KL-22 (Rl0N (made by Lee Ang Co., Ltd.))

44242 9 V. Description of the invention (14)), and the number of particles above 0.2 " m which is dissolved and immersed in the aforementioned ultrapure water is determined. The following formula (4), which is the same as formula (1), is used to calculate the number of particles (particulate / m 1) in ultrapure water in order to obtain the cleanliness caused by ultrapure water. In Table 1, the aforementioned measurement results are shown. [Formula 4] The number of particles in the water (a / m 1) = the calculated number (a) X the amount of water in ultrapure water 2000 (ml) sample size 5 (ml) X container capacity 4000 (ml) ~ ..... ( 4) As shown in Table 1, the initial cleanliness was 12 pieces / m 1, that is, the dissolution and leaching system of the impurities was very rare. [Table 1] Cleanliness of test items (pieces / m 1)) Weight reduction rate (%) Content solution Ultrapure water resist A EGA Initial storage conditions] Months after 2 3 ° C 6 months 4 0 ° C 3 Example 1 Inner container A 1 2 15 24 < 0,01 < 0.0 1 Example 2 Inner container B 15 13 25 < 0.0 1 < 0.0 1 Comparative Example 1 PTFE inner bag C 110 265 3 58 < 0.0 1 < 0.01 LDPE inner bag D 25 75 2656 3 290 0.01 0.02 Comparative Example 2 Metal container 273 656 863 < 0,01 < 0.01 Glass bottle 1797 34 1 506 < 0.0 1 < 0.01 Next , Put 2 liters of this novolac tree containing cresol

8811S465.ptd Page 17 4424 2 9

And the solid content of the perylene I-based sulfonate-based photosensitizer, and the positive photoresist (resistor A) composed of ethyl acetate cellosolve, and The formula (5) is the same as described above, so as to obtain the so-called cleanliness. In addition, in Table 丨, the aforementioned two results are shown. j [Formula 5] The number of particles in the resist solution (pieces / ml) ==! L ^ number (pieces) X amount of choke solution 2000 (ml) sample size 5 (ml) X container capacity 4000 (ml). .... (5)

J. In addition, once again, the aforementioned container was hermetically closed by a screw cap ', and it was left at room temperature for one month. Under the condition that no air bubbles are generated, the container that has been left for 1 month is rotated 3 times, and the photoresist solution in the container is frolled, and the photoresist solution of 5rol is used to shake the moon. The description of the J-plane is the same, and the number of particles in the photoresist solution, (a / ml) is calculated in order to obtain the cleanliness after 1 month. In the display = the above-mentioned results are determined. A, it's like a watch! As shown, the initial cleanliness of the inhibitor A is ^ == month, and the cleanliness is 24 / ml. Therefore, the second leaching system of impure particles is very rare. Then 'Place 4 liters of ethyl acetate cellosolve (EGA) in the container 嗲 容 Ξ ί In the state that the container is completely closed by a screw cap, the temperature of "time to 23. ° and 40. ° constant temperature In the chamber, in order to determine the weight reduction of the 6-acid ethylcellosolve caused by changes in time and time (%

Page 18 IIM, 4424 2 9 V. Description of the invention (16)). In Table 1, the aforementioned measurement results are shown. As shown in Table 1, the weight reduction after 6 months under '23 c is 0.01% or less, and the weight reduction after 3 months under 40 is 0.01% or less. Therefore, the weight Extinction is very rare. In addition, put 4 liters of ethyl acetate cellosolve into the container 'and in a state where the container is completely closed by a screw cap, the 3 Haier device is maintained in a 2VP planting medium' in order to In 1CP-MS (HP_4500 (manufactured by Chikusei Co., Ltd.), the gold ion concentration of the ethyl acetate cellosolve was measured for 6 months. Table 2 does not show the measurement results described below. [Table 2] — __ yg 禅 禅 [Yu Zhilang, F 1 A 1 »v) Xf \ 1 · flue ZO. W5 N a K Ca M g Γ Fe _ A \ < 0.1 < 0.1 1 < 0.1 Grab J / Λ 1 < 〇.i < 0.1 < 0.1 * Example 1 Inner container A < 0 * inside < 0. 1 1 Λ 1 < 0.1 < 0 .Tj c 0. 1 < 0.1 < 0.1 Example 2 Inner container < 0.1 " Γ. 1 < 0.1 0.3 < 0. 1 < 0.1 < 0. 1 Ft comparative example & comparative example 2 PTF EI inner male Γ < 0.1 < 0.1 —0 · 1 < 0. 1 < 0.1 LDPE inner bag D metal container pumping sauce < 〇. P < 0.1 1 3 < 0.1H < 0.1 < 0.1 〇_ i < 0.1 0 · 7 < 0.1 < 0.1 < 0.1 < 0.1 0.3 0.2 cO. I < 0.1 0.2 0.1 < 〇'l < 0.1 In addition, As shown in Table 2, after 6 months of storage treatment, no increase in the concentration of metal ions was observed. In order to investigate the infiltration due to the organic dissolution from the inner container A, The effect of the phenomenon on the coating performance of the photoresist liquid 'so' use '

44242s V. Description of the invention (17) The device "and" also uses a rotary applicator, and applies the resist solution after 23 weeks of storage treatment at 23 t to a silicon wafer 'so that To check the film thickness and applicability of photoresist (with or without pinholes and streaks). In Table 3 ', the aforementioned measurement results are shown. [Table 3] Storage time of the resist ~~ — · Film thickness (μm) Comprehensive judgment of the coating performance Coating resist A 〇 Time 1.001 Good Resist B 1 week later ----- 1.002 Good Good-Room 1.002 Good Good-. ---- 1 week later 1. 003 Good good pregnancy in Table 3 表, thin limb acne in Da. Towels & & 丄 ,,-^. .Nnn,-long叩 巧. Fork buckle concept After applying the high-purity chemical liquid container shown in Babaojing m rotation speed 1 to the coating solution through a middle tank, the photoresist solution was coated on a silicon wafer. The light of 5 νΛ for the 1-minute pre-baking treatment under test L was taken into consideration. Therefore, the allowable value of the change in film thickness is the phenomenon of the first two. 4 'Good gastric applicability " No streaks and pinholes. The "good" in the comprehensive judgment of the coating performance indicates that its coating property is quite good. In addition, there is no air bubble mixed into the resist A, and the photoresist is homogeneous: stable, so that it can be obtained fairly uniformly. Finally, the performance of the resist A is investigated. Using a rotary applicator,

8811S465.ptd See page 20, 44242 9 V. Description of the invention (18) ------ According to the specified conditions, the resist A produced immediately and the resist A after 3 months of storage It is coated on a silicon aa circle which has been cleaned by a general method, and is also baked for 1 minute by a 90 C heating plate. Next, it is made by using an I-ray stepper.着 Exposure processing. _, A heating plate at 110 ° C, and the wafer obtained above was subjected to a baking treatment for 1 minute. An alkaline developing solution (2 38% = methyl ammonium argon oxide aqueous solution) is used for these wafers to perform a developing process to obtain a positive pattern. The performance of the obtained positive pattern resolution, the actual sensitivity, the film residual rate, the presence or absence of dross (with imaging residue), and the various properties of the adhesion between the positive pattern and the silicon wafer Evaluation was performed "In Table 4, the results of the aforementioned measurement are shown. As shown in Tables 3 and 4, the coating performance and resolution, effective sensitivity, film residual rate, and presence of scum (with imaging residue) in the photoresist solution, as well as the positive circular pattern and Various properties of the adhesion between the silicon wafers did not change significantly, and the resist A did not deteriorate after long-term storage. (Example 2) The film formed of the high-density polyethylene used in Example 1 was used as the inner side, and also a multilayered film (from the outer side) of nylon, which was commercially available, was used. 6, 6 / Adhesive resin / Low-density polyethylene = 20/10/30 (Atm)) to cover the outside so as to be a double bag, and the rest are processed by the same treatment as in Example 1 Out of container B. This polyethylene made by blow molding

ggU8465.ptd Page 21, 4424 2 9 V. Description of the invention (19) Inside the rigid container (content: 4 liters), the aforementioned container B is set. The cleanliness, weight change (%), and metal ion concentration were measured in the same manner as in Example 1. Tables 1 and 2 show the aforementioned measurement results. As shown in Table 1, the cleanliness in water is 15 / ml, the cleanliness in resist B is 13 / m1, and the cleanliness after 1 month is 25 / m. 1 'Therefore, the dissolution and leaching of impurities is extremely rare. Then the weight reduction amount after 6 months at 23 ° C was 0.01% or less, and the weight reduction amount after 3 months at 40 ° C was 0.01% or less, so 'weight reduction amount Departments are very rare. In addition, as shown in Table 2, at 23. (: Next, after 6 months of storage treatment, no increase in metal ion concentration was found. Then 'cut the 1 x 4 cm corner of the carcass part of the aforementioned rigid polyethylene container except for rigid' 〇 (Transmittance 1) by a spectrophotometer (model: ubset — 55 (manufactured by Japan Spectrum Co., Ltd.)) in order to determine the absorbance at a wavelength of 900-200 nm. When the absorbance at 600 nm is 7. 〇 4%), and when the absorbance at 400 nm is 70 (transmittance 10-5%), it can show quite good light-shielding properties. The thickness of the sample at this time is 3, 6 7 mm. The resist A prepared in Example 1 was replaced with the solid component of the basic soluble resin containing a phenol methyl alcohol varnish resin as a main component and a diazide sulfonate-based photosensitizer, and The positive photoresist (resistor B) composed of 2_heptanone solvent is convenient for implementation

i ^ ο ο V. Description of the invention (20) Similarly, the so-called coating performance was investigated, and the measurement results of "showing the front block" are shown in Table 3. In addition, the photoresist was also investigated in the same manner as in Example 1. Performance, and the resolution of the positive pattern obtained, the actual sensitivity, the residual film rate, and the presence of scum (with imaging residue), and the adhesion between the positive pattern and the silicon wafer Various performances were evaluated. Table 4 shows the measurement results described above. As shown in Tables 3 and 4, the coating performance and resolution of the photoresist solution, the actual sensitivity, the thin film residual rate, and the presence or absence of scum (with imaging residue), and the positive pattern and Various properties of the adhesion between the silicon wafers did not change significantly, and the photoresist y liquid did not deteriorate after long-term storage. [Table 4] Retention time resolution (V m) Sensitivity (msec) Residual film rate (%) Presence or absence, scum-adhesive resist A 0 time 0.35 350 100 No good after 3 months 0.35 350 100 No good inhibitor B 〇 Time 0. 30 370 100 No good after 3 months 0.30 370 100 No good (Comparative Example 1) In the case of the pedestal, polytetrafluoroethylene (PTFE) was used to make the inner bag C. ^ 'Borrow / In The density of 5.86% by weight 924g / cra3' Melting index 丨 .50% B = 1 = 1 and the weight average molecular weight 1 > < 10% lower than polymer Density n eight magic) in order to make the inner bag D. The inner bag c and the inner bag D are respectively set in a too outer container made of stainless steel as in the first embodiment.

笫 Page 23 4424 2 9

5. Description of the invention (The 2U system is the same as in Example 1 to determine the cleanliness, weight reduction (%), and metal ion concentration. In Tables 1 and 2, the foregoing measurement results are shown. As shown in the table As shown in Table 1 and Table 2, it was found that the cleanliness of the water in the inner bag C made of polytetrafluoroethylene (PTFE) was 11 pieces / ml, and the cleanliness in the tincture was 2 6 5 / M 1, and the cleanliness after 1 month is 3 5 8 / m 1. Therefore, there are many dissolved and leached systems of impurities, and calcium and iron ions are also dissolved. : The cleanliness of water in inner bag D made of low-density polyethylene (LDPE) is 2575 pieces / ml, the cleanliness in photoresist is 2656 pieces / mi, and the cleanliness after 1 month is 3 2 900 / m 1 'Therefore, there are very many choices for the dissolution of impure particles, and it also dissolves ..., iron ions, and the system.' Then, as shown in Table 1, it should be due to polytetrafluoroethylene. Weight reduction (%) of ethyl acetate cellosolve caused by time-lapse treatment of inner bag C made of dilute (PTFE) Weight loss after 6 months at 23 t A small amount is less than 0.01%, and 40T: the weight reduction after 3 months is less than 0.01%, so the weight reduction is very scarce. On the other hand, it was found that: The weight reduction (%) of the ethyl caproate cellosolve caused by the time-lapse treatment of the inner bag D made of low-density polyethylene (LDPE) is the weight reduction after 6 months at '23C. Therefore, the amount of weight loss after 3 months at ^ 40 eC is 0.02%, so that the right solvent infiltration occurs. Μ As described above, within the range of polytetrahexene (PTFE) Bags and low-density polyethylene (LDPE) inner bags 'system' valleys to dissolve quite a lot of particles and metal ions

88118465.ptd Page 24 4424 2 9 V. Description of the invention (22) The photoresist is contaminated and cannot be used as a container for the photoresist solution. (Comparative Example 2) A metal (SUS304 (non-ferrous steel)) container and a glass bottle were used. In the same manner as in Example 1, the cleanliness, absorbance, weight change (%), and metal ion concentration were measured. Tables 1 and 2 show the aforementioned measurement results. Just as shown in Table 1, 'the cleanliness in water of the metal container is 273 pieces / ml', the cleanliness in the photoresist A is 6 56 pieces / mi, and the cleanliness after 1 month is 8 6 3 / m 1, so 'the dissolution and leaching system of impure particles is very much', and it also dissolves a lot of iron ions and nickel ions β ^ The cleanliness of water in glass bottle is 1 797 / ml, photoresist The cleanliness in Agent A is 3 41 pieces / m 1, and the cleanliness after 1 month is 506 pieces / m 1. Therefore, there are very many dissolving and leaching systems of impurities, and they also dissolve out. Quite a lot of sodium ions. As mentioned above, metal containers and glass containers dissolve a considerable amount of impurities and metal ions, so that the photoresist is contaminated and cannot be used as a container for the photoresist solution. [Effects of the Invention] As explained in detail above, the container for the high-purity chemical liquid of the present invention is stored and transported in the high-purity chemical liquid, and there is no dissolution and leaching of particles and metal ions. , And can maintain the quality of high-purity chemical liquid. In addition, the inner container of the container for a high-purity chemical liquid of the present invention is not easily broken and has flexibility, and therefore, the inner container can be taken out from the outer container relatively easily. Also, you can borrow

'4 424 2 9 V. Description of the invention (23). The exchange operation of the liquid-feeding unit and the sealing cover is performed so that the germanium storage and discharge operation of the high-purity chemical liquid can be performed easily and safely 3 [ Description of the component numbers] a: Ventilation path b: Ventilation path C: Ventilation path d: Ventilation path 2: Inner container 3: Outer container 1: High-purity chemical liquid 6: 7: Welding part handle 1 1 plus Pressure source 12 Connector 13 Connector cover 14 Ventilation hole 15 Plug 16 Liquid discharge pipe 16A: Liquid discharge pipe 16B: Liquid discharge pipe 17 Airtight holder 19 Check valve 20 Inner container mouth

Porphyry 118465, ptd Page 26 442 4 2 q V. Description of the invention (24)

21 Mouth part of outer container 22 Cut σ 23 Male key code 24 Female key code 25 Middle bolt 26 Ribbon nut 27 Fixing piece 28 Bracket 29 Tubular bracket 30 Ventilation hole 31 Opening and closing cover 32 Pad 33 Gasket 34 Gasket 35 Ventilation hole 36 Ventilation hole 8811B465, ptd Page 27: 4424 2 9 Brief description of the drawings [Simplified description of the drawings] FIG. 1 is a container for displaying a high-purity pharmaceutical liquid of the present invention An overall view of the embodiment. Fig. 2 is a schematic diagram showing an inner container of a container for a high-purity chemical liquid. FIG. 3 is a cross-sectional view of a main part showing a container for a high-purity chemical liquid. Fig. 4 is a cross-sectional view 显示 of a lid for opening and closing a container for a high-purity chemical liquid.

SiinS465.ptd Page 28

Claims (1)

-4424 2 9 VI. Scope of patent application 1. A kind of high-quality polyene and the device, which are intermediary, and inserted into the outer container of the content, the system is 2. If it is located in the inner container holder, the system is a holder The screw section's outer 3. If the application is to separate the point and the intubation is also provided with the internal and content action that is only used to hold the handle. 4 · If you apply for the collection of liquids in the smoke system, such as 5-, please request the purity of the medicinal hydrocarbon system before storage. On the way to the inside of the so-called holding liquid exchange ground screw device patent fan outlet monk purity patent $ Ει container for product liquid, which is characterized by: the inner container described in the soft inner container formed by purity resin The airtightness of the independent container is freely hermetically and openly connected to the liquid discharge pipe connected with a check valve in the air between the two, and the inner container is hermetically sealed. In addition, the connection to the Canada Connector for pressure source. The 1¾-purity music product container for item 1 above, wherein the mouth of the air-tight outer container for holding the aforementioned liquid discharge pipe is 'and' the air-tight opening and closing action, so that the outer The container is freely carrying out the above-mentioned hermetically sealed container for high-purity drug liquid of item 2, and the lower part of the container in the liquid discharge pipe # connected to the check valve. J The upper cover for opening and closing, and the aforementioned airtight cover for removing the upper part of the body-discharging tube 4 is connected to the mouth portion of the outer container so that outer = $ 保 部, for the outside world The above-mentioned pull device is closed, and the container for the high-purity high-quality liquid of the second item of Meiwei is closed. The airtight holder is made of the high purity of the third item formed by the same resin as the inner container. Container for pharmaceutical liquid, wherein 88118465.ptd Scope of Patent Application No. 29-Six 'ί The liquid discharge pipe and the air-tight holder and / or the opening and closing device ^ are formed of a polyolefin-based high-purity resin of the same quality as the inner container. The container for high-purity pharmaceutical liquids for which the scope of patent application No. 1 is applied, among which 5 & smoke-based high-purity resins are made of ethylene, propylene, butene _ 1, 4_ , Or a thin smoke polymer of -1. At least one selected from the copolymers of olefins other than 0 and ethylene. 11: The container for high-purity pharmaceutical liquids in the fourth item of the scope of profit, in which «Xuan & dilute hydrocarbon-based high-purity resin 1 is used as a reason. Ethylene, propylene, butene-1, 4_, and 2 are polymers of olefins such as dihexene-1 or octene-1. At least one selected from the copolymers of dilute hydrocarbons other than dilute hydrocarbons, such as the high-purity pharmaceutical liquid-side polyolefin-based high-purity resins such as those in the scope of patent application No. 5, are based on $, f-based-pentyl-buhex Dilute-丨, bite is Xin = ,: dilute, butadiene-1, 4_ = a copolymer selected from ethylene and olefins other than ethylene 0 / Page 30