KR102355132B1 - Containers with active surface and methods of forming such containers - Google Patents

Abstract

an enclosure member; and optionally, an article that is at least partially within the enclosure member. The enclosure member and/or article comprises an activated polymeric surface, wherein the activated polymeric surface is formed by a method comprising treating the sulfonated polymeric surface with a composition comprising a protic acid. A method of forming a container is also provided. Containers and methods of their formation find particular use in the electronics industry and in the storage of high purity chemicals useful in the water, pharmaceutical and food and beverage industries.

Description

CONTAINERS WITH ACTIVE SURFACE AND METHODS OF FORMING SUCH CONTAINERS

FIELD OF THE INVENTION The present invention relates generally to containers for high purity materials. More particularly, the present invention relates to active containers for high-purity materials and methods for making such active containers. The present invention finds particular applicability not only in the water, food and pharmaceutical industries, but also in the packaging and storage of materials (electronic materials) used in the manufacture of electronic devices, specifically materials used in the semiconductor manufacturing industry.

In the semiconductor manufacturing industry, process chemical containing liquids are used throughout the manufacturing process, for example, in lithography, coating, cleaning, stripping, etching, and chemical mechanical planarization (CMP) processes. Such chemicals include, for example, acids, solvents, photoresists, antireflective materials, developers, removers, slurries, and cleaning solutions. With the continued reduction of critical dimensions required for advanced semiconductor devices, it has become increasingly important for process chemicals to be provided in ultrapure form. However, process chemicals even in purified form contain trace amounts of metals such as iron, sodium, nickel, copper, calcium, magnesium and potassium, among others. The presence of metals in process chemicals can be detrimental, affecting device reliability and product yield, for example, by leading to patterning defects and alteration of electrical properties of the formed device. Sources of these metallic impurities may be derived from raw materials used in chemical manufacturing processes, or may otherwise be introduced during manufacturing and packaging processes.

Reduction of metals and other impurities from process chemicals, raw materials and precursors has conventionally been achieved through the use of ion-exchange and/or filtration processes. After such purification, the chemical is typically packaged in a container, such as a bottle or other vessel, which is then shipped to and stored by the end user. In the semiconductor manufacturing industry, chemical vessels are often piped directly to process tools used in wafer processing to reduce the potential for chemical contamination. However, it has been found that the chemical vessel itself can be a source of impurities, which may be created in situ during storage and transportation. Movement of containers, such as those occurring during transport, is thought to exacerbate this problem. In an effort to reduce particle generation in process chemicals, the use of a bottle comprising a fluorinated liner has been proposed, for example, in US Patent Application Publication No. 2013/0193164 A1. However, for environmental reasons, avoidance of fluorine-containing materials is desired. Moreover, these liners are passive materials and, at best, only contribute to the total metal in the formulation. It would be desirable to provide a container that actively removes such impurities from the contained chemicals, beyond contributing to the total metals in the container material. In addition to the electronics industry, such containers are preferred for use in, for example, the water, food and pharmaceutical industries.

Accordingly, there is a need in the art for improved containers and methods of making and using the same, which address one or more problems associated with the state of the art.

According to a first aspect of the present invention, a container is provided. The container may include an enclosure member; and optionally, an article at least partially within the enclosure member. The enclosure member and/or article comprises an activated polymeric surface, wherein the activated polymeric surface is formed by a method comprising treating the sulfonated polymeric surface with a composition comprising a protic acid.

According to a further aspect of the present invention, a method of forming a container having an activated polymeric surface is provided. The method includes providing an enclosure member or an enclosure member liner comprising a sulfonated polymeric surface, and treating the sulfonated polymeric surface with a composition comprising a protic acid. The present containers and methods of their formation find particular use in the manufacture of electronic devices (ie electronic materials), in the electronics industry, specifically in the semiconductor manufacturing industry, and in the storage of useful chemicals in the water, pharmaceutical and food industries. Electronic materials and other materials that can be stored in the containers of the present invention are typically high-purity materials, preferably ultra-pure materials.

The terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the invention. The singular forms "a", "an" and "the" are intended to include the singular and the plural, unless the context dictates otherwise.

The invention will now be described with reference to the drawings in which like reference numerals denote like features.
1 shows a container according to the invention comprising an activated enclosure member.
2 shows a container according to the present invention comprising an activated liner.
3a to 3e show a vessel according to the present invention having various activated texturized surface geometries.
4 and 5 show a container according to the invention comprising an activated insert.

The container of the present invention comprises an activated polymeric surface effective to remove metallic impurities from a chemical composition contained within the container. Suitable containers include, for example, those used for storage of high purity chemicals useful in the electronics industry. Such chemicals include, for example, acids, solvents, photoresists, antireflective materials, developers, removers, slurries, and cleaning solutions. Containers find further uses, for example in the water, pharmaceutical and food industries. Containers can take a variety of forms, such as bottles, cans, boxes, drums and tanks.

The method of the present invention for activating the polymeric surface of a container will now be described. It is understood that a component comprising a polymeric surface may take a variety of forms, wherein at least a portion of the activating surface will be in contact with the chemical composition stored within the container. The polymeric surface to be activated comprises, for example, an enclosure member liner, or an insert, which is at least partially disposed within the enclosure member, or an inner wall of the enclosure member.

Suitable materials for the surface to be activated include organic polymers capable of being sulfonated. These polymers have a hydrogen atom bonded to a carbon group, wherein the sulfur can be replaced by a sulfonic acid group bonded directly to the carbon atom. Preferably the polymeric material is a thermoplastic, non-aromatic, hydrocarbon polymer having a linear carbon-carbon backbone molecular structure with only non-aromatic substituents and a plurality of free hydrogen atoms attached to carbon atoms of the polymer chain. These polymers are extruded or molded to form enclosure members, liners or inserts. Examples of such thermoplastic extrusion grade or moldable grade non-aromatic hydrocarbon polymers include homopolymers of ethylene, propylene, isobutylene, methyl-pentene-1, butene-1, vinyl chloride, vinylidene chloride, acrylonitrile, interpolymers of monomers with each other, chlorinated polyethylene and chlorinated polypropylene, and blends of the aforementioned monomers and copolymers. Of particular interest are high and low density polyethylenes, polypropylenes, ethylene/propylene copolymers, ethylene/butene-1 copolymers and blends thereof.

The polymer composition may include one or more optional additives selected, for example, from antioxidants, pigments, dyes, or extenders known in the art. Typically these optional additives, if used, are present in the composition in minor amounts, such as 0.01 to 10% by weight, based on the total solids of the polymer composition.

The polymeric surface is activated through a multi-step process comprising sulfonation and treatment of the sulfonated polymeric surface with a composition comprising a protic acid. Activation of the polymeric surface allows metal impurities to be removed from the chemical composition disposed within the vessel in contact with the activated surface. Without wishing to be bound by any particular theory, it is believed that metal impurities are removed from the chemical composition by adsorption and/or ion exchange by the activated polymer surface. The process chemicals described herein used to treat polymeric surfaces, such as sulfonated materials, protic acid-containing compositions and other materials that may be used in the process, such as rinses, are preferably less than 100 ppb per metal. , more preferably less than 50 ppb per metal, most preferably less than 10 ppb per metal.

Sulfonation of polymeric surfaces may be effected by techniques well known in the art. It should be understood that the desired extent of sulfonation to be used will depend to some extent on the material being stored in the container and the particular polymer being sulfonated. A degree of sulfonation that is too low leads to inefficient removal of metallic impurities from the material to be disposed within the container, whereas an excessive degree of sulfonation can lead to a significant loss of the tensile strength of the member being sulfonated, which can lead to degradation of the polymer. have. Typically, the degree of sulfonation is from 0.5 to 25 atomic %, preferably from 1 to 15 atomic %, more preferably from 3 to 10 atomic %, based on the total carbon atoms on the surface of the sulfonated polymer. A suitable sulfonation temperature will depend on the particular technique used, but in any method should be below the melting point of the processing substrate and the polymeric material. Similarly, the pressure at which the sulfonation is effected will depend on the particular sulfonation process and is typically atmospheric, but may be sub-atmospheric (e.g. 10-750 Torr) or above-atmospheric pressure (e.g. 770-4000 Torr). . The sulfonation reaction time can vary considerably depending on the method and other variables, with times from 2 minutes to 24 hours being typical.

A typical method of sulfonation of a polymeric surface of a substrate to be activated is exposing such surface to gaseous sulfur trioxide, preferably diluted with a dry inert gas such as air, argon, nitrogen, helium, carbon dioxide, sulfur dioxide, etc. . The concentration of sulfur trioxide in the gaseous sulfonating agent may vary from 0.1% by volume to 50% by volume of sulfur trioxide, preferably from 5% by volume to 35% by volume, based on the total gaseous sulfonating agent. Sulfur trioxide can be produced in situ by reacting sulfur dioxide with air in a catalyst bed, such as vanadium oxide (V ₂ O _{5 ) or other catalyst beds known in the literature.} The sulfonation time required to produce an acceptable degree of sulfonation depends on the concentration and temperature of sulfur trioxide. For example, the degree of sulfonation increases with higher concentrations of sulfur trioxide and higher temperatures. It may be desirable to exclude water vapor from the gas by means of a conventional dryer tube, since in the presence of water in liquid or vapor form the sulfur trioxide is converted into droplets of sulfuric acid of varying concentrations, so that sulfonation of plastics can be inhibited or prevented. . For removal of water, it may also be desirable to purge the sulfonation chamber with a dry inert gas such as air, argon, nitrogen, helium, carbon dioxide, sulfur dioxide, or the like prior to introduction of the sulfonation reactant. The rate of addition of the gas(s) should be controlled to maximize the rate of sulfonation while minimizing any potential adverse effects such as melting of the polymer. The gas(s) may be added to the sulfonation chamber containing the substrate in a continuous or discontinuous manner, for example in discrete pulses. The reaction chamber may be at ambient pressure, or a pressure less than or greater than ambient pressure. The reaction temperature for the gas phase sulfonation reaction is typically from 20 to 132°C.

Additional methods suitable for sulfonation of polymeric surfaces include subjecting the surface to an inert liquid solvent such as a liquid polychlorinated aliphatic hydrocarbon such as methylene chloride, carbon tetrachloride, perchlorethylene, 1,1,2,2-tetrachloroethane, or contacting with a solution of SO _{3 in ethylene dichloride.} Suitable concentrations include, for example, 1 to 25% by weight of SO ₃ , based on the total solution. The reaction temperature is typically between 0 and 140° C., with it being understood that the temperature should be lower than the melting point of the polymer being treated.

A further suitable sulfonation method comprises contacting the polymeric surface with a chlorosulfonic acid sulfonating agent. The polymeric surface may be sulfonated with, for example, neat chlorosulfonic acid. Optionally, chlorosulfonic acid may be used in combination with one or more additional solvents, for example liquid polychlorinated aliphatic hydrocarbons such as methylene chloride, carbon tetrachloride, perchlorethylene, 1,1,2,2-tetrachloroethane, or ethylene dichloride. have. Typical temperatures for this sulfonation process are 25-75°C.

A further suitable sulfonation method comprises contacting the polymeric surface with sulfuric acid. A suitable concentration is not particularly limited. Sulfuric acid may be, for example, in concentrated or non-concentrated form. Suitable concentrations include, for example, at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 90 wt%, at least 96 wt%, or at least 98 wt% sulfuric acid. The concentration of sulfuric acid may alternatively be up to 96% by weight. The reaction temperature for sulfonation with sulfuric acid is typically from 0 to 140°C, for example from 30 to 120°C.

A further suitable sulfonation method comprises contacting the polymeric surface with fuming sulfuric acid.

As used herein, fuming sulfuric acid (also referred to as “oleum”) differs from concentrated sulfuric acid in that it is 100% sulfuric acid containing _{dissolved SO 3 .} The use of expressed sulfuric acid can be advantageous compared to concentrated sulfuric acid, since fuming sulfuric acid has a significantly greater reactivity and thus the sulfonation reaction occurs faster. Typically, the concentration of fuming sulfuric acid is described in weight percent _{of free SO 3 in solution.} Typical fuming sulfuric acid is 0.1 to 30% by weight SO ₃ in solution. The reaction temperature for oleum sulfonation is typically from 0 to 140°C, for example from 30 to 120°C.

In the sulfonation process described herein, parameters of the sulfonation process include, for example, temperature, reactant concentration, pressure, sulfonation time and properties of the polymer, such as percent crystallinity, content of double bonds and porosity. It is generally known in the art. Determination of suitable conditions for the sulfonation methods described above to achieve the desired degree of sulfonation is within the level of one of ordinary skill in the art.

Typically, the sulfonated polymeric surface is treated with a rinsing agent, typically a water-miscible liquid, such as water, preferably deionized water (DI water), methanol, ethanol, It will be rinsed with acetone or tetrahydrofuran. The rinse agent may be a water-immiscible liquid, for example toluene, dichloromethane or an ether, such as methyl tert-butyl ether, diethyl ether, diamyl ether or other C2-C10 dialkylethers. Such rinsing is useful to remove residual unbound acid. Rinsing is typically done for a period of time reaching neutrality, ie, until the rinse material already used exhibits the same pH level as the rinse material not in contact with the sulfonated polymeric surface. The rinsing process is typically done by filling the article to be rinsed, emptying the contents, for example in the case of an enclosure member or liner, and repeating until neutrality is reached. In another embodiment, the protic acid solution may be applied by immersing the article in a tank containing the protic acid solution and allowing the article to immerse, preferably by stirring. The protic acid solution may be applied to the tank continuously, or more typically, applied batchwise, such as by successively filling and draining the tank until neutral is reached.

Typically the sulfonation process discolors the treated polymeric surface, where a black or dark brown layer is produced. Without wishing to be bound by any particular theory, it is believed that this reaction is one of simultaneous oxidation and sulfonation. This discoloration appears to be the result of complex oxidation of the polymers such that the polymers contain chromogenic unsaturated polymer groups and oxidizing groups such as hydroxy, keto or carboxylic acid groups of various polymers. It is also believed that these groups condense with each other to form additional chromophores responsible for the dark color shown above.

It is typically desired to remove or reduce the chromic layer, as it can leach into and contaminate the material to be stored in the container. For this purpose, the discolored surface may optionally be rinsed with a bleaching agent. Suitable decolorizing agents include, for example, aqueous solutions of sodium hypochlorite, aqueous solutions of calcium hypochlorite, aqueous solutions of hydrogen peroxide, aqueous solutions of ammonium percarbonate, aqueous solutions of potassium persulfate, aqueous solutions of potassium permanganate and aqueous solutions of sodium dichromate. Typically, bleaching of polymeric surfaces is followed by rinsing with a water-miscible liquid such as those described above to remove residual bleach, reaction by-products and other contaminants.

The sulfonated polymeric surface is then treated with a composition comprising a protic acid. By treatment with a protic acid, contaminants and metals generated in the sulfonation process can be removed. Suitable protic acids include, for example, nitric acid, hydrochloric acid, sulfuric acid, acetic acid, citric acid, tartaric acid, iminodiacetic acid, phosphoric acid, boric acid, or combinations thereof. Preferably, the polymeric surface is contacted with a liquid solution of a protic acid. The concentration of the protic acid solution is typically from 1 to 80% by weight of acid, preferably from 10 to 30% by weight of acid. The protic acid solution fills the substrate, such as for example for treatment of the inner polymeric surface of an enclosure member or liner, and for a desired period of time contact between the protic acid and the polymeric surface is desired, preferably using agitation. It can be applied to the article by allowing it. Alternatively, the protic acid solution may be applied by immersing the article in a tank containing the protic acid solution and allowing the article to immerse, preferably by stirring. Rinsing times of 1 hour to 14 days, preferably 5 to 10 days, are typical. The temperature of the acid rinse is typically from 0 to 100°C, preferably from 20 to 50°C.

The protic acid treatment may alternatively be done in a closed chamber using a protic acid in gaseous or vapor phase form. Suitable protic acids in gaseous form include, for example, hydrogen chloride and hydrogen fluoride. Protic acids suitable for use in vapor form include those described above with respect to protic acid solutions. Steam generation can be accomplished using methods known in the art, for example by bubbling an inert carrier gas such as air, argon, nitrogen or helium into the protic acid solution and, optionally, heating the acid. have. Treatment times of 1 hour to 14 days, preferably 5 to 10 days, are typical. Typically, the treatment may be conducted at atmospheric or superatmospheric pressure. Before treating the sulfonated article with the protic acid in this method, the polymeric surface must be treated with an aqueous rinse agent, typically deionized water, to solubilize and remove metal contaminants from the polymeric surface during contact with the protic acid. . The rinsing treatment may be done prior to introduction into the closed chamber, such as by filling the article with a rinse agent or immersing the article in the rinse agent. The rinse time is not critical and the treatment should be sufficient to create a water film on the polymeric surface to be treated with the protic acid.

If bleaching of the polymeric surface is desired, the bleaching can be done concurrently with a protic acid treatment instead of or in addition to a separate bleaching process as described above. In decolorization during protic acid treatment, certain protic acids themselves, such as nitric acid, can function as decolorizing agents. Optionally, a bleaching agent other than the protic acid may be used in combination with the protic acid to treat the polymeric surface. Suitable protic acid/bleaching agent combinations include, for example, any combination of said protic acid and bleaching agent. Particularly suitable combinations include, for example, hydrogen peroxide/sulfuric acid, hydrogen peroxide/hydrochloric acid, hydrogen peroxide/nitric acid and sodium dichromate/sulfuric acid. The protic acid-treated polymeric surface is typically rinsed with an aqueous-miscible rinse agent as described above with respect to rinsing after the sulfonic acid treatment. Rinsing is typically done for a time to reach neutrality.

Optionally, the protic acid-treated polymeric surface can be treated with an agent that neutralizes sulfonic acid groups on the polymer. This may be required, for example, to prevent a reaction if the material to be stored in the container is not compatible with the acid groups. In this case, neutralization of the acid groups can make the container compatible with the material to be stored. The neutralizing agent may be, for example, in liquid or vapor phase. Suitable liquid neutralizing agents include, for example, primary, secondary or tertiary amines, ammonium hydroxides, including quaternary ammonium hydroxide solutions such as tetramethyl ammonium hydroxide; primary, secondary, or tertiary immigration; or mixtures thereof. Suitable amines that may be used are primary, secondary or tertiary saturated aliphatic amines of 2 to 5 carbon atoms which are water soluble and are usually liquid at room temperature, for example amylamine, dipropylamine, triethylamine, diethylamine, ethylamine; diethylmethylamine, ethanolamine, diethanolamine, triethanolamine and thioethanolamine. Suitable imines that may be used include primary, secondary or tertiary aromatic and aliphatic imines that are water soluble and normally liquid at room temperature, such as pyridine, pyrimidine and pyrazine.

The sulfonated plastic surface may be immersed in the aqueous solution or suspension, or the solution may be sprayed, washed with water and dried. Typically, the neutralizing agent is added to the water in an amount such that the resulting solution contains 1-20% by weight of the neutralizing agent. The contact time is not critical, and a simple dipping or spraying may suffice. The temperature at which the neutralization takes place is not critical and is typically -20 to 60°C, preferably 20 to 40°C.

Suitable vapor phase neutralizing agents include, for example, gaseous ammonia, methylamine, dimethylamine, trimethylamine and pyridine. For materials that are in liquid form under standard conditions, such as pyridine, the material may be heated to a temperature that permits evaporation. The contact time between the vapor phase neutralizer and the sulfonated polymeric surface is typically from 1 minute to 24 hours, more typically from 15 minutes to 4 hours. The temperature at which vapor phase neutralization is carried out is typically from 0 to 100°C, preferably from 20 to 80°C. Upon selective neutralization treatment, the polymeric surface is typically rinsed with an aqueous-miscible rinse agent such as those described above with respect to rinsing after the sulfonic acid treatment.

An exemplary container according to the invention will now be described with reference to the drawings. 1 shows an exemplary first container 1 according to the invention. The container (1) includes a polymeric enclosure member (2) having an active inner surface (3) effective to remove metallic impurities from a composition to be stored therein. The polymeric enclosure member may be made by processes well known in the art, for example by extrusion blow molding. The enclosure member is formed of a polymer as described above that aids in sulfonation. The inner surface of the enclosure member is activated via a method as described above. The container 1 further comprises a stopper 4 for covering the lid of the enclosure member. Suitable closures are known in the art and include, for example, screw caps, press-fit caps, dispense connectors (eg, ErgoNOW™ connectors from Entegris, Inc.) and Includes plugs with bulkheads. To accommodate the closure, the bottle may include a mating feature to secure the lid, such as a screw thread.

2 shows an exemplary second container 1 according to the present invention comprising a polymeric liner 6 having an active inner surface 7 for removing metallic impurities from a composition stored therein. Liners may be made by processes well known in the art, for example by extrusion blow molding. The liner is formed of a polymer as described above which aids in sulfonation. The inner surface of the liner is activated via a method as described above. For containers comprising a polymeric liner 6 , the enclosure member may be constructed of a material other than a polymer as described herein. The enclosure member may be made of, for example, glass, stainless steel, or other inert, clean material that is not contaminated.

To increase the interaction between the activated polymeric surface and the chemical composition to be stored in a container, it may be desirable to provide an activated polymeric surface with increased surface area for greater contact with the chemical composition. It is believed that this increased activated polymeric surface area may further reduce metal contaminants. Increased surface area can be achieved, for example, through surface texturing of the polymeric surface. Suitable textures include various geometries of convex or indented structures, such as dimples, domes, ridges, grooves, pyramids, rectangular cuboids, cylinders, and combinations thereof. Surface texturing may be accomplished during manufacture of the bottle (or other enclosure member or article). 3A shows a container 1 with an enclosure member 2 having a texturized activation surface 8A. 3B-3E illustrate various types of texturized surfaces, including pyramid (FIG. 3B), rectangular cuboid (FIG. 3C), dome (FIG. 3D) and dimple (FIG. 3E) texturing.

In the above exemplary container, the enclosure member or liner comprises an active inner polymeric surface. Additionally or alternatively, the container may include an insert disposed at least partially within an enclosure member comprising an activated polymeric surface for metal removal. In order to increase the area of the activated surface of the insert, it may be desirable to include surface texturization on the insert, such as that described in connection with FIGS. 3A-3E .

4 shows an exemplary container 1 comprising an activated polymeric bottom closure cylindrical insert 10 disposed within an enclosure member 2 . Activation of the polymeric insert is via methods such as those described herein. To maximize the surface area of the active polymeric surface, it is preferred that each of the exposed surfaces of the cylindrical assembly be activated. Cylindrical assemblies can be made by methods known in the art, for example by extrusion blow molding.

5 shows a further exemplary container 1 comprising an activation insert in the form of an activated elongate polymeric member 12 . The polymeric member 12 may be, for example, hollow or solid, and may be of a variety of elongated shapes, such as cylindrical or prismatic, with a cylindrical shape being typical. The member 12 may be manufactured by methods known in the art, for example extrusion blow molding followed by activation via a method as described herein. The polymeric member 12 may be integral with the closure 4 as shown, or may be provided as a separate component from the closure.

The following non-limiting examples are illustrative of the present invention.

Example

Example 1

Gas phase sulfonation was applied to a 15 ml LDPE white translucent bottle (diameter of 2.4 cm, height of 5.8 cm). The pre-sulfonated bottle showed no measurable elemental sulfur, and the sulfonated bottle showed an elemental sulfur content at the surface of 6.9 atomic percent as determined by x-ray photoelectron spectroscopy (XPS). It was visually observed that the inside and outside of the sulfonated bottle was discolored black. The bottle was rinsed with DI water (18 MΩ). The sulfonated bottle was filled with 20% by weight of Optima™ nitric acid (Fisher Scientific) and the bottle was shaken for 7 days. The nitric acid turned yellow and the discoloration on the inner wall of the bottle was virtually eliminated, indicating removal of sulfonation by-products. The bottle was then rinsed with deionized water (18 MΩ), and the sulfur content at the surface as measured by XPS was 3.4 atomic %. 10 ml of OC™3050 Immersion Topcoat Material (Dow Electronic Materials, Marlborough, MA) (which contains a mixture of acrylic resin and organic solvent) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. ICP metal analysis included analysis of two samples from bottles in all instances. A result is shown in Table 1.

Comparative Example 1

A 15 ml LDPE white translucent bottle (diameter of 2.4 cm, height of 5.8 cm) was filled with 20% by weight of Optima™ nitric acid (Fisher Scientific), and the bottle was shaken for 7 days. The bottle was then rinsed with deionized water (18 MΩ). 10 ml of OC™3050 Immersion Topcoat Material (Dow Electronic Materials) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Comparative Example 2

Bottles rinsed with sulfonated/deionized water were prepared as described in Example 1. 10 ml of OC™3050 Immersion Topcoat Material (Dow Electronic Materials) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Example 2

A nitric acid-treated/deionized water rinse bottle was prepared as described in Example 1. 10 ml of TraceSELECT Ultra TMAH solution (25% by weight in water) (Fluka) was added to the bottle and shaken for 1 week. The TMAH solution obtained a dark brown color, which was removed from the bottle. The bottle was rinsed with 18 MOhm deionized water and 10 ml of OC™3050 Immersion Topcoat Material (Dow Electronic Materials) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Example 3

A nitric acid-treated/deionized water rinse bottle was prepared as described in Example 1. 10 ml of Optima ammonium hydroxide solution (20% by weight) (Fisher Scientific) was added to the bottle and shaken for 1 week. The TMAH solution obtained a dark brown color, which was removed from the bottle. The bottle was rinsed with 18 MOhm deionized water and 10 ml of OC™3050 Immersion Topcoat Material (Dow Electronic Materials) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Example 4

To study the suitability of the container for reuse of the present invention, the bottle prepared as in Example 1 (which was sulfonated, nitric acid-washed, and containing OC™3050 Immersion Topcoat Material (Dow Electronic Materials)) was distilled rinsed with ethyl lactate. The bottle was then rinsed with 18 MOhm deionized water and treated with 20 wt % Optima nitric acid (Fisher Scientific) for 7 days. The resulting nitric acid remained transparent. The bottle was rinsed with 18 MOhm deionized water and 10 ml of OC™3050 Immersion Topcoat Material (Dow Electronic Materials) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Example 5

Bottles rinsed with sulfonated/deionized water were prepared as described in Example 1. The bottle was filled with 98 wt % Optima sulfuric acid (Fisher Scientific) for 7 days. The resulting sulfuric acid still remained clear, and the bottle's inner wall remained black. The bottle was rinsed with 18 MOhm deionized water and 10 ml of OC™3050 Immersion Topcoat Material (Dow Electronic Materials) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Example 6

Bottles rinsed with sulfonated/deionized water were prepared as described in Example 1. The bottle was filled with a 1:4 mixture (by volume) of 30% by weight Optima hydrogen peroxide (Fisher Scientific):98% by weight of Optima sulfuric acid (Fisher Scientific), and the bottle was shaken for 7 days. The resulting sulfuric acid still remained transparent, and the color of the inner wall of the bottle lightened from black to brown. The bottle was rinsed with 18 MOhm deionized water and 10 ml of OC™3050 Immersion Topcoat Material (Dow Electronic Materials) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Example 7

Bottles rinsed with sulfonated/deionized water were prepared as described in Example 1. The bottle was filled with TraceSelect acetic acid (Fluka) and the bottle was shaken for 7 days. The resulting acetic acid still remained clear and the bottle's inner wall turned slightly brown. The bottle was rinsed with 18 MOhm deionized water and 10 ml of OC™3050 Immersion Topcoat Material (Dow Electronic Materials) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Comparative Example 3

A 15 ml LDPE white translucent bottle (diameter of 2.4 cm, height of 5.8 cm) was filled with 20% by weight of Optima™ nitric acid (Fisher Scientific), and the bottle was shaken for 7 days. The bottle was then rinsed with deionized water (18 MΩ). 10 ml of isoamyl ether (Toyo Gosei) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Example 8

A nitric acid-treated/deionized water rinse bottle was prepared as described in Example 1. 10 ml of isoamyl ether (Toyo Gosei) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Comparative Example 4

A 15 ml LDPE white translucent bottle (diameter of 2.4 cm, height of 5.8 cm) was filled with 20% by weight of Optima™ nitric acid (Fisher Scientific), and the bottle was shaken for 7 days. The bottle was then rinsed with deionized water (18 MΩ). 10 ml of ethyl lactate was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Example 9

A nitric acid-treated/deionized water rinse bottle was prepared as described in Example 1. 10 ml of ethyl lactate was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Comparative Example 5

A 15 ml LDPE white translucent bottle (diameter of 2.4 cm, height of 5.8 cm) was filled with 20% by weight of Optima™ nitric acid (Fisher Scientific), and the bottle was shaken for 7 days. The bottle was then rinsed with deionized water (18 MΩ). 10 ml of hydroxybutyric acid methyl ester (HBM) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Example 10

A nitric acid-treated/deionized water rinse bottle was prepared as described in Example 1. 10 ml of HBM was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Comparative Example 6

A 15 ml LDPE white translucent bottle (diameter of 2.4 cm, height of 5.8 cm) was filled with 20% by weight of Optima™ nitric acid (Fisher Scientific), and the bottle was shaken for 7 days. The bottle was then rinsed with deionized water (18 MΩ). 10 ml of propylene glycol monomethyl ether acetate (PGMEA) was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Example 11

A nitric acid-treated/deionized water rinse bottle was prepared as described in Example 1. 10 ml of PGMEA was added to the bottle. The bottle was shaken for 7 days and metal analysis was performed using an Agilent 8800 ICP-MS system. A result is shown in Table 1.

Claims (11)

A container for containing an ultrapure chemical composition, comprising:
no enclosure; and
optionally, an article at least partially within said enclosure member;
here,
wherein said enclosure member and/or article comprises an activated polymeric surface;
wherein said activated polymeric surface is formed by a method comprising sulfonating said polymeric surface and treating said sulfonated polymeric surface with a composition comprising a protic acid;
wherein said ultrapure chemical composition is in contact with said activated polymeric surface;
courage. The container of claim 1 , wherein the enclosure member comprises an activated polymeric surface. The container of claim 1 , wherein the article comprises an activated polymeric surface. 4. The container of claim 3, wherein the article is an enclosure member liner. 4. The container of claim 3, wherein the article is a container insert rather than an enclosure member liner. 6 . The vessel according to claim 1 , wherein the protic acid is selected from one or more of nitric acid, hydrochloric acid, sulfuric acid, or acetic acid. The container according to any one of claims 1 to 5, wherein the ultrapure chemical composition is water, a pharmaceutical, a food, a beverage, or an electronic material. A method of forming a container having an activated polymeric surface, the method comprising:
providing an enclosure member or enclosure member liner comprising a polymeric surface;
sulfonating the polymeric surface; and
treating the sulfonated polymeric surface with a composition comprising a protic acid. The method of claim 8 , wherein the protic acid is selected from one or more of nitric acid, hydrochloric acid, sulfuric acid, or acetic acid. 9. The method of claim 8, wherein the composition comprising a protic acid further comprises an oxidizing agent other than the protic acid. 11. The method of any one of claims 8-10, further comprising, after treating the sulfonated polymeric surface with a composition comprising a protic acid, treating the polymeric surface with a base. , Way.

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