阅读说明：本技术 具有活性表面的容器以及形成此类容器的方法 (Container having an active surface and method of forming such a container ) 是由 A·鲁金科 E·J·胡可坎恩 G·波勒尔斯 于 2019-06-11 设计创作，主要内容包括：本文提供了容器,所述容器包含：外壳构件；以及任选地至少部分在所述外壳构件内的制品。所述外壳构件和/或所述制品包含活化的聚合物表面,其中所述活化的聚合物表面通过包括用包含质子酸的组合物处理磺化的聚合物表面的方法形成。还提供了形成容器的方法。所述容器及其形成方法在电子工业中以及在水、制药和食品和饮料工业中有用的高纯度化学品的储存中特别有用。(Provided herein is a container comprising: a housing member; and optionally an article at least partially within the housing member. The shell member and/or the article comprise an activated polymer surface, wherein the activated polymer surface is formed by a process comprising treating a sulfonated polymer surface with a composition comprising a protic acid. Methods of forming the container are also provided. The container and method of forming the same are particularly useful in the electronics industry and in the storage of high purity chemicals useful in the water, pharmaceutical and food and beverage industries.)

1. A container, comprising:

a housing member; and

an article optionally at least partially within the housing member;

wherein the shell member and/or the article comprises an activated polymer surface, wherein the activated polymer surface is formed by a process comprising treating a sulfonated polymer surface with a composition comprising a protic acid.

2. The container of claim 1, wherein the housing member comprises an activated polymer surface.

3. The container of claim 1 or 2, wherein the article comprises an activated polymeric surface.

4. The container of claim 3, wherein the article is an outer shell member liner.

5. The container of claim 3, wherein the article is a container insert that is not lined by a shell member.

6. The container of any one of claims 1 to 5, wherein the container contains an ultrapure chemical composition in contact with the activated surface.

7. The container of any one of claims 1 to 6, wherein the container contains water, a pharmaceutical, a food, a beverage, or an electronic material in contact with the activated surface.

8. A method of forming a container having an activated polymer surface, the method comprising providing an outer shell member or an outer shell member liner comprising a sulfonated polymer surface, and treating the sulfonated polymer surface with a composition comprising a protic acid.

9. 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.

10. The method of claim 8 or 9, wherein the composition comprising a protic acid further comprises an oxidizing agent different from the protic acid.

11. The method of any one of claims 8 to 10, further comprising treating the polymer surface with a base after treating the sulfonated polymer surface with a composition comprising a protic acid.

Background

The present invention generally relates to containers for high purity materials. More particularly, the present invention relates to active containers for high purity materials and methods of making such active containers. The invention is particularly suitable for packaging and storing materials used in the manufacturing of electronic devices (electronic materials) and in particular in the semiconductor manufacturing industry as well as in the water, food and pharmaceutical industries.

In the semiconductor manufacturing industry, liquid-containing process chemicals are used throughout the manufacturing process, for example, in photolithography, coating, cleaning, stripping, etching, and Chemical Mechanical Planarization (CMP) processes. Such chemicals include, for example, acids, solvents, photoresists, antireflective materials, developers, release agents (removers), pastes, and cleaning solutions. With the continuing reduction in critical dimensions required for advanced semiconductor devices, it is becoming increasingly important to provide process chemicals in ultra-pure form. However, even in purified form, process chemicals typically contain trace amounts of metals, such as iron, sodium, nickel, copper, calcium, magnesium, and potassium, among others. The presence of metals in the process chemistry can be detrimental, for example, creating patterning defects and altering the electronic properties of the resulting device, thereby affecting device reliability and product yield. The source of such metal impurities may be from raw materials used in chemical manufacturing processes, or may be otherwise introduced during the manufacturing and packaging processes.

Reduction of metals and other impurities from process chemicals, raw materials and precursors has conventionally been achieved by using ion exchange and/or filtration processes. After such purification, the chemicals are typically packaged in containers, such as bottles or other vessels, which are then shipped to and stored by the user. In the semiconductor manufacturing industry, these chemical containers are often communicated directly to the process tools used for wafer processing to reduce the possibility of contaminating the chemicals. However, it has been found that these chemical containers themselves can be a source of impurities that may be generated in situ during storage and transportation. It is believed that movement of the container, such as during transport, exacerbates this problem. In an effort to reduce particle generation in process chemicals, the use of bottles containing fluorinated liners has been proposed, for example, in U.S. patent application publication No. 2013/0193164a 1. However, avoiding fluorine-containing materials is desirable for environmental reasons. Furthermore, such liners are passivating materials and preferably do not contribute to the total metal in the formulation. It would be desirable to provide a container that, in addition to not contributing to the total metal in the container material, actively removes such impurities from the contained chemicals. In addition to the electronics industry, it is also desirable to use such containers 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 that address one or more of the problems associated with the prior art.

Disclosure of Invention

According to a first aspect of the present invention, a container is provided. These containers comprise: a housing member; and optionally an article at least partially within the housing member. The shell member and/or the article comprise an activated polymer surface, wherein the activated polymer surface is formed by a process comprising treating a sulfonated polymer surface with a composition comprising a protic acid.

According to another aspect of the invention, a method of forming a container having an activated polymer surface is provided. These methods include providing an outer shell member or an outer shell member liner comprising a sulfonated polymer surface, and treating the sulfonated polymer surface with a composition comprising a protic acid. These containers and methods of forming the same are particularly useful in the electronics industry in the manufacture of electronic devices (i.e., electronic materials), particularly in the semiconductor manufacturing industry, and in the storage of chemicals useful in the water, pharmaceutical, and food industries. The electronic materials and other materials that may be stored in the container of the present invention are typically high purity materials, and are preferably ultra pure materials.

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

Drawings

The present invention will be described with reference to the following drawings, wherein like reference numerals denote like features, and in which:

FIG. 1 illustrates a container according to the present invention including an activated shell member;

FIG. 2 illustrates a container according to the present invention including an activated liner;

3A-3E illustrate containers according to the present disclosure having different activated textured surface geometries; and

figures 4 and 5 show a container according to the invention comprising an activated insert.

Detailed Description

The container of the present invention comprises an activated polymer surface effective for removing metallic impurities from a chemical composition contained within the container. Suitable containers include, for example, those used in the storage of high purity chemicals useful in the electronics industry. Such chemicals include, for example, acids, solvents, polymers, photoresists, antireflective materials, developers, release agents, slurries, and cleaning solutions. These containers are further useful in, for example, the water, pharmaceutical and food industries. These containers may take various forms, for example, bottles, cans, boxes, drums, and tanks.

The method of the present invention for activating the polymeric surface of a container will now be described. The component comprising the polymeric surface may take a variety of forms, it being understood that at least a portion of the activated surface will be in contact with the chemical composition stored in the container. The polymeric surface to be activated may, for example, comprise an inner wall of the shell member, a shell member lining, or an insert to be at least partially disposed within the shell member.

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

The polymer composition may comprise one or more optional additives selected from, for example, antioxidants, pigments, dyes, or extenders as are known in the art. Such optional additives, if used, are typically present in the composition in small amounts, such as from 0.01 to 10 wt%, based on the total solids of the polymer composition.

The polymer surface is activated by a multi-step process comprising sulfonation and treatment of the sulfonated polymer surface with a composition comprising a protic acid. Activation of the polymer surface allows for the removal of metallic impurities from a chemical composition disposed within a container contacting 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 ion exchange and/or adsorption with activated polymer surfaces. The process chemicals described herein (e.g., sulfonated materials, protonic acid-containing compositions, and other materials that may be used in the process, such as rinse agents) for treating polymer surfaces are preferably less than 100ppb per metal, more preferably less than 50ppb per metal, and most preferably less than 10ppb per metal.

Sulfonation of the polymer surface may be carried out by techniques well known in the art. It will be appreciated that the desired range of sulfonation to be used will depend to some extent on the material stored in the container and the particular polymer being sulfonated. Too low a degree of sulfonation will result in ineffective removal of metal impurities from the material to be disposed within the container, while excessive sulfonation may result in a significant loss of tensile strength of the sulfonated member, which may result in decomposition of the polymer. Typically, the degree of sulfonation is from 0.5 to 25 atomic%, preferably from 1 to 15 atomic%, and more preferably from 3 to 10 atomic%, based on the total carbon atoms on the sulfonated polymer surface. Suitable sulfonation temperatures will depend on the particular technique used, but any method should be less than the melting point of the substrate and polymeric material being treated. The pressure at which sulfonation is similarly conducted will depend on the particular sulfonation process, and is typically atmospheric, but may be subatmospheric (e.g., 10 to 750 torr) or superatmospheric (e.g., 770 to 4000 torr). Sulfonation reaction times can vary significantly depending on the process and other variables, with times from two minutes to 24 hours being typical.

A typical method of sulfonating the polymer surface of the substrate to be activated is to expose such surface to gaseous sulfur trioxide, preferably diluted with a dry inert gas such as air, argon, nitrogen, helium, carbon dioxide, sulfur dioxide, and the like. The concentration of sulfur trioxide in the gaseous sulfonating agent can vary from 0.1 to 50 vol%, preferably from 5 to 35 vol% of sulfur trioxide based on the total gaseous sulfonating agent. Sulfur trioxide can be produced by passing sulfur dioxide and air over a catalyst bed such as vanadium (V) oxide₂O₅) Or other catalyst bed reactions known in the literature. The sulfonation time required to produce an acceptable degree of sulfonation varies with sulfur trioxide concentration and temperature. For example, the degree of sulfonation increases with higher concentrations of sulfur trioxide and higher temperatures. It may be desirable to remove water vapor from the above gases through conventional desiccant tubes because, in the presence of water in liquid or vapor form, the sulfur trioxide is converted into droplets having varying concentrations of sulfuric acid, and sulfonation of the plastic may be inhibited or prevented. To remove water, it may further be desirable to purge the sulfonation chamber with a dry inert gas such as air, argon, nitrogen, helium, carbon dioxide, sulfur dioxide, and the like, prior to introducing the sulfonation reactants. The rate of addition of the one or more gases should be controlled to maximize the sulfonation rate while minimizing any potential adverse effects, such as melting of the polymer. The one or more gases may be introduced into the sulfonation chamber containing the substrate continuously or in a discontinuous manner, such as in different 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 ℃.

Another suitable method for sulfonating polymer surfaces includes in an inert liquid solvent such as a liquid polychlorinated aliphatic hydrocarbon (e.g., methylene chloride, carbon tetrachloride, perchloroethylene, 1)2, 2-tetrachloroethane, or ethylene dichloride) with SO₃Is contacted with the solution of (a). Suitable concentrations include, for example, from 1 to 25 wt% SO based on total solution₃. The reaction temperature is typically from 0 ℃ to 140 ℃, it being understood that the temperature is less than the melting point of the polymer being treated.

Another suitable sulfonation method includes contacting the polymer surface with a chlorosulfonic sulfonating agent. The polymer surface can be sulfonated, for example, with pure chlorosulfonic acid. Optionally, chlorosulfonic acid may be used with one or more additional solvents, for example, liquid polychlorinated aliphatic hydrocarbons such as methylene chloride, carbon tetrachloride, perchloroethylene, 1, 2, 2-tetrachloroethane, or ethylene dichloride. Typical temperatures for this sulfonation process are from 25 ℃ to 75 ℃.

Another suitable sulfonation method includes contacting the polymer surface with sulfuric acid. Suitable concentrations are not particularly limited. The sulfuric acid may, for example, be in concentrated or non-concentrated form. Suitable concentrations include, for example, 10 wt% or more, 20 wt% or more, 30 wt% or more, 90 wt% or more, 96 wt% or more, or 98 wt% or more sulfuric acid. The concentration of sulfuric acid may alternatively be 96 wt% or less. The reaction temperature for sulfonation with sulfuric acid is typically from 0 ℃ to 140 ℃, e.g., from 30 ℃ to 120 ℃.

Another suitable sulfonation method includes contacting the polymer surface with oleum. As used herein, fuming sulfuric acid (also known as "oleum") is different from concentrated sulfuric acid in that oleum contains dissolved SO₃100% sulfuric acid. The use of oleum may be advantageous compared to concentrated sulfuric acid, since oleum is significantly more reactive and thus sulfonation reactions occur more rapidly. Typically, the concentration of oleum is described as free SO in solution₃Wt% of (A). Typical oleum is 0.1 wt% to 30 wt% SO in solution₃. The reaction temperature for the sulfonation of oleum is typically from 0 ℃ to 140 ℃, e.g., from 30 ℃ to 120 ℃.

For the sulfonation processes described herein, it is generally known in the art that variables of the sulfonation process include, for example, temperature, reactant concentrations, pressure, sulfonation time, and polymer properties such as percent crystallinity, double bond content, and porosity. It is within the level of skill in the art to determine the appropriate conditions for the sulfonation process described above to achieve the desired degree of sulfonation.

Typically, the sulfonated polymer surface will be rinsed with a rinsing agent, typically a water miscible liquid such as water, preferably Deionized (DI) water, methanol, ethanol, acetone, or tetrahydrofuran, to remove residual sulfuric acid, reaction by-products, and other contaminants. The rinse may be a water immiscible liquid (e.g., toluene, methylene chloride) or an ether (e.g., methyl tert-butyl ether, diethyl ether, dipentyl ether, or other C2-C10 dialkyl ethers). Such rinsing is useful for removing residual unbound acid. Rinsing is typically performed for a period of time to reach neutrality, i.e., until the used rinsing material exhibits the same pH level as the rinsing material that has not been contacted with the sulfonated polymer surface. The rinsing process is typically carried out by filling the article being rinsed, for example in the case of a housing member or liner, emptying the contents and repeating until neutrality is reached. In another aspect, the protic acid solution may be applied by immersing the article in a tank containing the protic acid solution and soaking the article, preferably under agitation. The protic acid solution may be applied to the cell in a continuous manner or, more typically, in a batch manner, such as by continuously filling and emptying the cell until neutrality is reached.

The sulfonation process typically results in discoloration of the treated polymer surface, wherein a black or dark brown layer results. Without wishing to be bound by any particular theory, it is believed that this reaction is a simultaneous oxidation and sulfonation reaction. The discoloration thus appears to be a result of complex oxidation of the polymer, such that it contains unsaturated polymeric groups of various chromophores and oxidized groups, such as hydroxyl, keto, or carboxylic acid groups. It is further believed that these groups condense with each other to form additional chromophoric groups that contribute to the dark colors noted above.

It is typically desirable to remove or reduce the discoloration layer, as the discoloration layer may penetrate 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 bleaching agents include, for example, aqueous solutions of sodium hypochlorite, calcium hypochlorite, hydrogen peroxide, ammonium percarbonate, potassium persulfate, potassium permanganate, and sodium dichromate. Bleaching of the polymer surface is then typically followed by rinsing with a water-miscible liquid as described above to remove residual bleach, reaction by-products and other contaminants.

The sulfonated polymer surface is then treated with a composition comprising a protic acid. Contaminants and metals resulting from the sulfonation process may be removed by treatment with a protic acid. 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 polymer 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, and preferably from 10 to 30% by weight of acid. The protonic acid solution may be applied to the article, for example, by filling a substrate such as that used to treat the interior polymer surface of the shell member or liner and allowing contact between the protonic acid and the polymer surface for a desired period of time, preferably under agitation. Alternatively, the protic acid solution may be applied by immersing the article in a tank containing the protic acid solution and soaking the article, preferably under stirring. Rinsing times of from one hour to 14 days, preferably from 5 days to 10 days, are typical. The temperature of the acid rinse is typically from 0 ℃ to 100 ℃, preferably from 20 ℃ to 50 ℃.

The protonic acid treatment may alternatively be carried out in a closed chamber using a protonic acid in a gas or vapor phase. Suitable protic acids in gaseous form include, for example, hydrogen chloride and hydrogen fluoride. Suitable protic acids for use in the vapor form include those described above with respect to protic acid solutions. Vapor generation can be accomplished using methods known in the art, such as bubbling an insert carrier gas, such as air, argon, nitrogen, or helium, into the protic acid solution and optionally heating the acid. Treatment times of from one hour to 14 days, preferably from 5 days to 10 days, are typical. Typically, these treatments may be carried out at atmospheric or superatmospheric pressure. Prior to the protonic acid treatment of the sulfonated article in this process, the polymer surface should be treated with an aqueous rinse, typically deionized water, to allow for the dissolution and removal of metal contaminants from the polymer surface during contact with the protonic acid. The rinsing treatment may be carried out before introduction into the closed chamber, for example by filling the article with a rinsing agent or by immersing the article in a rinsing agent. The rinsing time is not critical and the treatment should be sufficient to produce a film of water on the polymer surface to be treated with the protic acid.

If bleaching of the polymer surface is desired, it may be carried out simultaneously with the protonic acid treatment instead of or in addition to a separate bleaching process as described above. For bleaching during protonic acid treatment, certain protonic acids themselves (e.g., nitric acid) may act as bleaching agents. Optionally, a bleaching agent other than a protic acid may be used in combination with the protic acid to treat the polymer surface. Suitable protonic acid/bleaching agent combinations include, for example, any combination of the aforementioned protonic acids and bleaching agents. Particularly suitable combinations include, for example, hydrogen peroxide/sulfuric acid, hydrogen peroxide/hydrochloric acid, hydrogen peroxide/nitric acid, and sodium dichromate/sulfuric acid.

The protonic acid treated polymer surface is typically rinsed with a water miscible rinsing agent as described above for post-sulfonic acid treatment rinsing. Rinsing is typically performed for a period of time to achieve neutrality.

Optionally, the protonic acid treated polymer surface may be treated with an agent that neutralizes sulfonic acid groups on the polymer. This may be desirable, for example, to prevent reactions in which the material to be stored in the container is incompatible with the acid groups. In this case, neutralization of the acid groups can render the container compatible with the material to be stored. The neutralizing agent may be, for example, in the liquid or vapor phase. Suitable liquid phase neutralizing agents include, for example: primary, secondary or tertiary amines; ammonium hydroxide, including quaternary ammonium hydroxide solutions, such as tetramethylammonium hydroxide; a primary, secondary or tertiary imine; or mixtures thereof. Suitable amines that may be used include primary, secondary, or tertiary saturated aliphatic amines having 2 to 5 carbon atoms that are water soluble and are typically liquid at room temperature, for example, pentylamine, 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 are typically liquid at room temperature, such as pyridines, pyrimidines, and pyrazines.

The sulfonated plastic surface may be immersed in an aqueous solution or suspension, or it may be sprayed with a solution, washed with water and dried. Typically, the neutralizing agent is added to the water in an amount such that the resulting solution contains from 1 wt% to 20 wt% neutralizing agent. The contact time is not critical and only dipping or spraying may be sufficient. The temperature at which the neutralization is carried out is not critical and is typically from-20 ℃ to 60 ℃, preferably from 20 ℃ to 40 ℃.

Suitable vapor phase neutralizers include, for example, gaseous ammonia, methylamine, dimethylamine, trimethylamine, and pyridine. For those materials that are in liquid form under standard conditions, such as pyridine, the material may be heated to a temperature that allows evaporation. The contact time between the vapor phase neutralizer and the sulfonated polymer surface is typically from 1 minute to 24 hours, and more typically from 15 minutes to four hours. The temperature at which the vapor phase neutralization is carried out is typically from 0 ℃ to 100 ℃, preferably from 20 ℃ to 80 ℃. If optional neutralization treatment occurs, the polymer surface is typically rinsed with a water-miscible rinsing agent as described above with respect to post-sulfonic acid treatment rinsing.

Exemplary containers according to the invention will now be described with reference to the accompanying drawings. Fig. 1 illustrates a first exemplary container 1 according to the present invention. The container 1 includes a polymeric housing member 2 having an active interior surface 3 effective for removing metallic impurities from a composition to be stored in the container. The polymeric housing member may be manufactured by methods well known in the art, such as extrusion blow molding. The housing member is formed from a polymer that facilitates sulfonation as described above. The inner surface of the housing member is activated by the method as described above. The container 1 further comprises a closure 4 for covering the housing member. Suitable closures are known in the art and include, for example, screw caps, press-fit caps, dispensing connectors (e.g., ErgoNOW, Inc.) from integer corporation^TMAttachment) and closures with membranes. To accommodate the closure, the bottle may include mating features, such as threads, for securing the cap.

Fig. 2 illustrates a second exemplary container 1 according to the present invention comprising a polymeric liner 6 having an active interior surface 7 for removing metallic impurities from a composition stored in the container. The liner may be manufactured by methods well known in the art, such as extrusion blow molding. The liner is formed from a polymer that favors sulfonation as described above. The inner surface of the liner is activated by the method as described above. For containers containing a polymeric liner 6, the shell member may be constructed of materials other than polymers as described herein. The housing member may be made of, for example, glass, stainless steel, or other inert, clean material that is not contaminated.

In order to increase the interaction between the activated polymer surface and the chemical composition to be stored in the container, it may be desirable to provide the activated polymer surface with an increased surface area for greater contact with the chemical composition. It is believed that this increased activated polymer surface area may provide a further reduction in metal contamination. The increased surface area may be achieved, for example, by surface texturing of the polymer surface. Suitable textures include raised or recessed structures of various geometries, such as dimples, domes, ridges, grooves, pyramids, rectangular cuboids, cylinders, and combinations thereof. Surface texturing may be achieved during manufacture of the bottle (or other housing member or article). Fig. 3A shows a container 1 having a shell member 2 with a textured activation surface 8A. Fig. 3B-3E show various forms of textured surfaces including pyramidal (fig. 3B), rectangular cuboid (fig. 3C), dome (fig. 3D), and dimple (fig. 3E) texturing.

In the exemplary container described above, the outer shell member or inner liner includes an active inner polymer surface. Additionally or alternatively, the container may include an insert disposed at least partially within the housing member that includes an activated polymer surface for metal removal. For the purpose of increasing the activated surface area of the insert, it may be desirable to include surface texturing on the insert as described with respect to fig. 3A-3E.

Fig. 4 illustrates an exemplary container 1 comprising an activated polymer closed bottom cylindrical insert 10 disposed within a housing member 2. Activation of the polymer insert is performed by a method as described herein. Each exposed surface of the cylindrical component is preferably activated for the purpose of maximizing the surface area of the active polymer surface. The cylindrical assembly may be manufactured by methods known in the art, such as extrusion blow molding.

Fig. 5 illustrates another exemplary container 1 including an activated insert in the form of an activated elongate polymeric member 12. The polymeric member 12 may be, for example, hollow or solid in form, and may have various elongated shapes, such as cylindrical or prismatic, with cylindrical being typical. The member 12 may be manufactured by methods known in the art, such as extrusion blow molding, and subsequently activated by methods as described herein. The polymeric member 12 may be integral with the closure 4 as illustrated, or may be provided as a separate component from the closure.

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

Examples of the invention

Example 1

A15 ml LDPE white translucent bottle (2.4cm diameter, 5.8cm height) was subjected to gas phase sulfonation. The pre-sulfonated bottles exhibited no measurable elemental sulfur, and the sulfonated bottles exhibited an elemental sulfur content of 6.9 atomic percent at the surface as determined by x-ray photoelectron spectroscopy (XPS). The sulfonated bottle was visually observed to change color from inside to outside to a black color. The bottles were rinsed with Deionized (DI) water (18 megaohms). The sulfonated bottles were treated with 20 wt% Optima^TMNitric acid (Fisher Scientific) was filled and the bottles were shaken for 7 days. The nitric acid turned yellow in color and the discoloration on the inside wall of the bottle was substantially removed, indicating the removal of the sulfonated by-product. The bottle was then rinsed with DI water (18 megaohms) and the sulfur content at the surface as measured by XPS was 3.4 atomic percent. 10ml of OCTM3050 immersion topcoat material (March, Mass.) comprising a mixture of acrylic resin and organic solventThe Erberg Dow electronics (Dow electronic Materials, Marlborough, Mass.) was added to the jar. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. ICP metal analysis included analysis of two samples from the vial for all examples. The results are shown in Table 1.

Comparative example 1

A15 ml LDPE white translucent bottle (2.4cm diameter, 5.8cm height) was charged with 20 wt% Optima^TMNitric acid (feishel technologies) was filled and the bottles were shaken for 7 days. The bottle was then rinsed with DI water (18 megaohms). 10ml of OC are added^TM3050 immersion topcoat material (dow electronics) was added to the bottle. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Comparative example 2

sulfonated/DI water rinsed bottles were prepared as described in example 1. 10ml of OC are added^TM3050 immersion topcoat material (dow electronics) was added to the bottle. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Example 2

The nitric acid treated/DI water rinsed sulfonated bottles were prepared as described in example 1. 10ml of a TraceSELECT Ultra TMAH solution (25 wt% in water) (Furca Corp. (Fluka)) was added to the flask and shaken for one week. The TMAH solution acquired a dark brown color and was removed from the bottle. Rinse bottle with 18MOhm DI water and rinse 10ml of OC^TM3050 immersion topcoat material (dow electronics) was added to the bottle. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Example 3

The nitric acid treated/DI water rinsed sulfonated bottles were prepared as described in example 1. 10ml of Optima ammonium hydroxide solution (20 wt%) (Feishel technologies) was added to the bottle and shaken for one week. The TMAH solution acquired a dark brown color and was removed from the bottle. Rinse bottle with 18MOhm DI water and rinse 10ml of OC^TM3050 immersion topcoat material (dow electronics) was added to the bottle. The flask was shaken for 7 daysAnd metal analysis was performed with an agilent 8800ICP-MS system. The results are shown in Table 1.

Example 4

To investigate the suitability of reusing the vessel of the present invention, sulfonated, nitric acid washed and containing OC was rinsed with distilled ethyl lactate^TM3050 bottles of topcoat material (dow electronics) as prepared in example 1 were immersed. The vial was then rinsed with 18 MOhmDI water and treated with 20 wt% Optima nitric acid (fisher technologies) for 7 days. The nitric acid obtained remained clear. Rinse bottle with 18MOhm DI water and rinse 10ml of OC^TM3050 immersion topcoat material (dow electronics) was added to the bottle. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Example 5

sulfonated/DI water rinsed bottles were prepared as described in example 1. The bottles were filled with 98 wt% Optima sulfuric acid (Feishale technologies) for 7 days. The resulting sulfuric acid remained clear and the interior of the bottle wall remained black. Rinse bottle with 18MOhm DI water and rinse 10ml of OC^TM3050 immersion topcoat material (dow electronics) was added to the bottle. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Example 6

sulfonated/DI water rinsed bottles were prepared as described in example 1. The bottles were treated with 30 wt% Optima hydrogen peroxide (fisher technologies): a1: 4 mixture (by volume) of 98 wt% Optima sulfuric acid (Feishale technologies) was filled and the bottle was shaken for 7 days. The resulting sulfuric acid remained clear and the color of the inner bottle wall was reduced from black to brown. Rinse bottle with 18MOhm DI water and rinse 10ml of OC^TM3050 immersion topcoat material (dow electronics) was added to the bottle. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Example 7

sulfonated/DI water rinsed bottles were prepared as described in example 1. The vial was filled with TraceSelect acetic acid (fuluca) and shaken for 7 days.The resulting acetic acid remained clear and the interior of the bottle wall became slightly brownish. Rinse bottle with 18MOhm DI water and rinse 10ml of OC^TM3050 immersion topcoat material (dow electronics) was added to the bottle. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Comparative example 3

A15 ml LDPE white translucent bottle (2.4cm diameter, 5.8cm height) was charged with 20 wt% Optima^TMNitric acid (feishel technologies) was filled and the bottles were shaken for 7 days. The bottle was then rinsed with DI water (18 megaohms). 10ml of isoamyl ether (Toyo Gosei) was added to the bottle. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Example 8

The nitric acid treated/DI water rinsed sulfonated bottles were prepared as described in example 1. 10ml of isoamyl ether (Toyo Synthesis industries Co., Ltd.) was charged into a bottle. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Comparative example 4

A15 ml LDPE white translucent bottle (2.4cm diameter, 5.8cm height) was charged with 20 wt% Optima^TMNitric acid (feishel technologies) was filled and the bottles were shaken for 7 days. The bottle was then rinsed with DI water (18 megaohms). 10ml of ethyl lactate were added to the flask. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Example 9

The nitric acid treated/DI water rinsed sulfonated bottles were prepared as described in example 1. 10ml of ethyl lactate were added to the flask. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Comparative example 5

A15 ml LDPE white translucent bottle (2.4cm diameter, 5.8cm height) was charged with 20 wt% Optima^TMNitric acid (feishel technologies) was filled and the bottles were shaken for 7 days. Then DI water (18 mega ohm)The bottle was rinsed. 10ml of methyl Hydroxybutyrate (HBM) was added to the bottle. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Example 10

The nitric acid treated/DI water rinsed sulfonated bottles were prepared as described in example 1. 10ml of HBM was added to the flask. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Comparative example 6

A15 ml LDPE white translucent bottle (2.4cm diameter, 5.8cm height) was charged with 20 wt% Optima^TMNitric acid (feishel technologies) was filled and the bottles were shaken for 7 days. The bottle was then rinsed with DI water (18 megaohms). 10ml of Propylene Glycol Monomethyl Ether Acetate (PGMEA) was added to the flask. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

Example 11

The nitric acid treated/DI water rinsed sulfonated bottles were prepared as described in example 1. 10ml of PGMEA was added to the flask. The vial was shaken for 7 days and metal analysis was performed using an Agilent 8800ICP-MS system. The results are shown in Table 1.

TABLE 1

The metal content in parts per billion (ppb) is the average of two samples from a bottle; σ — standard deviation of two samples from a vial; "Y" -; "TC" — an immersion topcoat material; "IE" ═ isoamyl ether; "EL" ═ ethyl lactate; "HBM" ═ methyl hydroxybutyrate; "PGMEA" ═ propylene glycol monomethyl ether acetate; "nd" is not detected; vial reuse study.