Methods of making an antistatic agent

The present invention relates to a method for producing an antistatic agent.

Thermoplastics are useful in the manufacture of goods and components for a wide range of applications, from automotive parts to electronic devices. It is desirable to add an antistatic agent to the thermoplastic resin, especially for widespread use in electronic devices. Many polymers or polymer blends are relatively non-conductive and static charges can accumulate during polymer processing and use. The charged molded article may attract, for example, small dust particles, which may lead to a decrease in the transparency of the article, for example, and impair the smooth surface appearance. Static charges can also be a significant obstacle to the manufacturing process of such polymers.

An antistatic agent is a substance added to a polymer to reduce the tendency of the polymer to acquire an electrostatic charge or to promote the dissipation of such charges in the presence of an electric charge. Organic antistatic agents are usually hydrophilic or ionic. When present on the surface of a polymeric material, it promotes the movement of electrons and eliminates the accumulation of electrostatic charges. Antistatic agents have also been added to polymer compositions prior to processing into articles, which is also referred to as "internal application". The useful antistatic agent applied in this way is thermally stable and can migrate to the surface during processing.

A large number of antistatic agents containing surfactants as the main components have been studied and tried. Many have one or more disadvantages such as lack of compatibility with polymers (preventing uniform dispersion), poor thermal stability and / or poor antistatic properties. In particular, poor heat resistance can adversely affect the optical properties of engineering plastics such as aromatic polycarbonates.

However, certain phosphonium salts of certain sulfonic acids have proven to be useful antistatic agents. U.S. Pat. No. 4,943380 discloses that an antistatic composition containing 90-99.9% by weight of polycarbonate and 0.1 to 10% by weight of heat-resistant phosphonium sulfonate of the following general formula is used to reduce the electrostatic charge of polycarbonate. Has been done.

<chemistry num="1"><img file="JP4932702B2_D0001.tif" /></chemistry>In the formula, R is a linear or branched alkyl group having 1 to 18 carbon atoms, and R¹, R²And R³Are the same, each of which is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R⁴Is a hydrocarbon group having 1 to 18 carbon atoms.

US Pat. No. 6,194,497 discloses an antistatic resin composition (particularly a transparent resin composition) comprising a thermoplastic polymer and a halogenated medium or short chain alkyl sulfonate of a tetrasubstituted phosphonium cation. There is. In the production of the antistatic agent described in this US patent, the corresponding acid is produced by ion exchange of potassium haloalkyl sulfonate. The haloalkyl sulfonic acid is then reacted with tetrabutylphosphonium hydroxide to produce an antistatic agent.

The advantage of this synthetic method is that by using an ion exchange step during synthesis, a very pure product is obtained, and most halogenated compounds that can ultimately cause deterioration of the resin, such as polycarbonate. Or not included at all. However, although suitable for the intended purpose, this particular synthetic method also has some disadvantages. For example, the use of the ion exchange phase can increase process costs and produce waste that requires disposal. This synthetic method uses a potassium salt as a starting material, which is made from the corresponding sulfonyl fluoride. Due to the relatively low solubility of potassium peralkylsulfonate (eg, about 5% at 20 ° C), a water / ethanol mixture is required during the ion exchange phase. Since ethanol is flammable, it is necessary to take a great deal of safety measures during synthesis. In addition, it is important to choose the right water / ethanol. Excess alcohol can make the final product soluble in the reaction solvent and may require additional extraction steps to isolate the product.<patcit num="1"><text>U.S. Pat. No. 4943380</text></patcit><patcit num="2"><text>U.S. Pat. No. 6,194,497</text></patcit><patcit num="3"><text>U.S. Pat. No. 3,442,854</text></patcit><patcit num="4"><text>U.S. Pat. No. 4,050,57</text></patcit><patcit num="5"><text>U.S. Pat. No. 4038258</text></patcit><patcit num="6"><text>U.S. Pat. No. 4093589</text></patcit><patcit num="7"><text>U.S. Pat. No. 5,021473</text></patcit><patcit num="8"><text>U.S. Pat. No. 5051330</text></patcit><patcit num="9"><text>U.S. Pat. No. 5,112558</text></patcit><patcit num="10"><text>U.S. Pat. No. 5,178,214</text></patcit><patcit num="11"><text>U.S. Pat. No. 5,449709</text></patcit><patcit num="12"><text>U.S. Pat. No. 5,468,793</text></patcit><patcit num="13"><text>U.S. Pat. No. 5468973</text></patcit><patcit num="14"><text>U.S. Pat. No. 5,476,555</text></patcit><patcit num="15"><text>U.S. Pat. No. 5494952</text></patcit><patcit num="16"><text>U.S. Pat. No. 5,668,202</text></patcit><patcit num="17"><text>U.S. Pat. No. 6080483</text></patcit><patcit num="18"><text>U.S. Pat. No. 6080488</text></patcit><patcit num="19"><text>U.S. Pat. No. 6090907</text></patcit><patcit num="20"><text>U.S. Pat. No. 6,599,966</text></patcit><patcit num="21"><text>European Patent No. 0170259</text></patcit><patcit num="22"><text>European Patent No. 0230907</text></patcit><patcit num="23"><text>European Patent No. 0246825</text></patcit><patcit num="24"><text>European Patent No. 0266596</text></patcit><patcit num="25"><text>European Patent No. 0309622</text></patcit><patcit num="26"><text>European Patent No. 0897950</text></patcit><patcit num="27"><text>Japanese Unexamined Patent Publication No. 01-178554</text></patcit><patcit num="28"><text>Japanese Unexamined Patent Publication No. 07-188539</text></patcit><patcit num="29"><text>Japanese Unexamined Patent Publication No. 08-302165</text></patcit>

<p> Therefore, in the art, there is still a need for a more efficient production method (particularly one-step method) of an antistatic agent for phosphonium sulfonate, and a thermoplastic resin composition containing these antistatic agents. Further, it is desirable that such a method can produce an antistatic agent in good yield without adversely affecting the safety of the process and / or the purity of the product.</p>

<p> The other disadvantage in the art is the method for producing a sulfonic acid phosphonium salt of the following general formula (1), in which the compound of the following general formula (2) is replaced with the compound of the general formula (3) in an aqueous medium. It is eliminated by a method comprising mixing with and separating the product of equation (1) from the aqueous medium.</p><p><chemistry num="2"><img file="JP4932702B2_D0002.tif" /></chemistry>In the equation, each X is independently a halogen or hydrogen, provided that the molar ratio of halogen / hydrogen is greater than about 0.90, and r is less than 8 when q + r and p is not 0. On condition that it exceeds 0, p is 0 or 1, q and r are integers from 0 to about 7, and each R is independently a hydrocarbon group having 1 to about 18 carbon atoms.</p><p><chemistry num="3"><img file="JP4932702B2_D0003.tif" /></chemistry>In the formula, M is Li or Na and X, q, p and r are as defined above.</p><p><chemistry num="4"><img file="JP4932702B2_D0004.tif" /></chemistry>In the equation, Z is a halogen and R is as defined above.</p><p> In another embodiment, the method for producing a sulfonic acid phosphonium salt of formula (1) mixes the compound of the following general formula (4) with a stoichiometric excess of the compound of the general formula (5) in an aqueous medium. And the step of separating the product of formula (1) from the aqueous medium.</p><p><chemistry num="5"><img file="JP4932702B2_D0005.tif" /></chemistry></p><p><chemistry num="6"><img file="JP4932702B2_D0006.tif" /></chemistry>In the equation, X, q, p, r and R have the same meaning as in the equation (1).</p><p> In another embodiment, the method for producing the sulfonic acid phosphonium salt of the formula (1) is that sodium hydroxide and / or lithium hydroxide in an aqueous medium, the compound of the above general formula (4) and the general formula (3). It comprises a step of mixing with the compound and a step of separating the phosphonium sulfonate of the formula (1) from the aqueous medium. In these equations, X, q, p, r and R are as defined above.</p><p> Another embodiment comprises an antistatic agent of formula (1) produced by any of the methods described above.</p><p> In another embodiment, there is provided a thermoplastic resin composition comprising a thermoplastic polymer and an antistatic agent produced by any of the methods described above.</p>

The present inventors unexpectedly can easily produce a haloalkyl sulfonic acid phosphonium salt suitable for use as an antistatic agent from a corresponding tetraalkyl phosphonium halide and a lithium haloalkyl sulfonic acid or sodium salt in an aqueous medium in one step. I got the knowledge. Alternatively, the haloalkyl sulfonic acid phosphonium salt can also be prepared in one step in an aqueous medium from the corresponding tetraalkylphosphonium halide or hydroxide and haloalkylsulfonyl fluoride. The reactants are readily available and the use of water as the reaction solvent facilitates product isolation. Thus, as a very beneficial and unexpected feature, we have found that the target antistatic molecule can be precipitated in high yield by simply mixing the reactants.

In general, the haloalkyl sulfonic acid phosphonium salt has the following general formula (1).

<chemistry num="7"><img file="JP4932702B2_D0007.tif" /></chemistry>In the formula, X is independently selected from halogen and hydrogen, provided that the halogen / hydrogen molar ratio exceeds about 0.90. Halogen can be selected independently from bromine, chlorine, fluorine and iodine. Specifically, the halogen is fluorine.

Further, in equation (1), p is 0 or 1, and q and r are 0 to about 7, provided that q + r is less than 8 and r exceeds 0 when p is not 0. Is an integer of. In one embodiment, p is 0.

Each R in the formula (1) is independently a hydrocarbon group having 1 to about 18 carbon atoms. That is, each R is the same or different, and may be a linear or branched aliphatic hydrocarbon group having 1 to about 8 carbon atoms or an aromatic hydrocarbon group having 6 to about 18 carbon atoms. As used herein, the "aromatic group" includes a complete aromatic group, an aralkyl group and an alkaline reel group. In one embodiment, the three R groups of the organic phosphonium cation are the same aliphatic hydrocarbon group with 1 to about 8 carbon atoms or the same aromatic hydrocarbon group with 6 to about 12 carbon atoms, 4 The second R group is a hydrocarbon group having 1 to about 18 carbon atoms.

Therefore, the present antistatic agent is a highly halogenated sulfonic acid phosphonium salt composed of an organic sulfonic acid anion and a tetrasubstituted organic phosphonium cation. A specific example is a perfluorocanoic salt, but due to the method for producing fluorination (electrolysis), a partially fluorinated compound may sometimes be produced.

Specific examples of suitable organic sulfonic acid anions include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoropentanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid and perfluorooctane. Sulfonic acid can be mentioned. A combination of these may be present.

Specific examples of the phosphonium cation include tetramethylphosphonium, tetraethylphosphonium, tetra-n-propylphosphonium, tetraisopropylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium, tributylethylphosphonium, trioctylmethylphosphonium and trimethylbutyl. Examples include cations such as phosphonium, trimethyloctylphosphonium, trimethyllaurylphosphonium, trimethylstearylphosphonium, triethyloctylphosphonium, tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium and tributylbenzylphosphonium. A combination of these may be present.

In one embodiment, the method for producing a phosphonium sulfonate of the formula (1), wherein the compound of the following general formula (2) is mixed with a stoichiometric excess of the compound of the general formula (3) in an aqueous medium. A method comprising a step of separating the product of the formula (1) and a step of separating the product of the formula (1) is provided.

<chemistry num="8"><img file="JP4932702B2_D0008.tif" /></chemistry>In the formula, M is an alkali metal selected from lithium (Li) and sodium (Na), and X, q, p and r are as defined above.

<chemistry num="9"><img file="JP4932702B2_D0009.tif" /></chemistry>In the equation, Z is a halogen and R is as defined above. In particular, Z is bromine or chlorine.

In one procedure, the method may include dissolving the sodium perhaloalkyl sulfonate or lithium salt of formula (2) in an aqueous medium. The aqueous medium may be substantially free of co-solvents such as ethanol. As used herein, "aqueous medium" means a solution, dispersion or suspension of water. Further, the "substantially free of co-solvent" aqueous medium used herein means that the co-solvent contained in the aqueous medium is less than about 1% by volume, specifically less than about 0.5% by volume, more specifically. Means less than about 0.1% by volume. Co-solvents may be used, which is necessary in the case of potassium salts, but the use of water that is substantially free of co-solvents results in high purity products due to the use of volatile solvents. Safety issues are avoided. When a co-solvent is used, suitable co-solvents promote the dissolution of sulfonic acid alkali salts and include lower alcohols such as methanol and ethanol and chlorinated solvents such as dichloromethane. A mixture of co-solvents can also be used.

An aqueous medium containing an alkaline salt of perhaloalkyl sulfonic acid may then be reacted with a tetra-substituted phosphonium halide. The order of addition does not seem to be important. For example, by dissolving the tetrasubstituted phosphonium halide in an aqueous medium and then adding an alkaline salt of perhaloalkyl sulfonic acid, by simultaneously dissolving and mixing the reactants, by dissolving the reactants separately and then mixing, etc. But the reaction is achieved. The sulfonic acid phosphonium salt obtained in the present invention can also be obtained by using a mixture of a perhaloalkylsulfonic acid alkali salt and a tetrasubstituted phosphonium halide.

The method can be carried out over a wide range of temperatures and reaction times, depending on the particular reactants used, co-solvents (if present), desired yields, desired purity, cost of production, convenience and ease of production. Dependent. For example, the temperatures in various processes are generally about 10 to about 100 ° C, specifically about 20 to about 95 ° C, and more specifically about 30 to about 90 ° C. In one embodiment, the reaction is carried out at room temperature or ambient temperature, which is generally about 20 to about 25 ° C. Similarly, the reaction time can vary, but is generally about 5 minutes to about 1 day, specifically about 30 minutes to about 12 hours, more specifically about 60 minutes to about 4 hours. These temperatures and times can be changed significantly and can be determined by one of ordinary skill in the art.

The tetrasubstituted phosphonium halide can be used in at least equimolar amounts with respect to the perhaloalkyl sulfonate. More specifically, the molar ratio of the perhaloalkyl sulfonate of formula (2) to the tetrasubstituted phosphonium halide of formula (3) is about 1: 1.001 to about 1: 1.5, specifically about 1: 1.002. ~ About 1: 1.1, more specifically about 1: 1.005 ~ about 1: 1.015. Optimal ratios may vary depending on the particular reactant, temperature, co-solvent (if present) and time, but can be readily determined by one of ordinary skill in the art.

In another embodiment, the molar ratio of the perhaloalkyl sulfonate of formula (2) to the tetrasubstituted phosphonium halide of formula (3) is from about 1.001: 1 to about 1.5: 1, specifically about 1.002: 1. ~ About 1.1: 1, more specifically about 1.005: 1 ~ about 1.015: 1. Optimal ratios may vary depending on the particular reactant, temperature, co-solvent (if present) and time, but can be readily determined by one of ordinary skill in the art.

As a very beneficial feature, the reactants and aqueous medium are selected so that the sulfonic acid phosphonium salt (1) precipitates from the aqueous medium in high purity and can be isolated from impurities (especially halogen-containing impurities) by simple filtration and washing. Will be done. Halogen-containing impurities (eg, tetrasubstituted phosphonium bromides and / or chlorides) are known to degrade resins such as polycarbonate, so it is particularly desirable to remove such impurities. Since such impurities are soluble in water, but the desired product is not soluble in water, the removal of impurities is easily and efficiently achieved by washing with water.

In another embodiment, in the method for producing phosphonium sulfonate of the formula (1), the sulfonyl fluoride of the following general formula (4) is used in an aqueous medium in a stoichiometric excess of the general formula (5). A method comprising mixing with a tetrasubstituted phosphonium hydroxide and separating the product of formula (1) from an aqueous medium is provided.

<chemistry num="10"><img file="JP4932702B2_D0010.tif" /></chemistry>In the formula, X, q, p and r have the same meaning as in the above case.

<chemistry num="11"><img file="JP4932702B2_D0011.tif" /></chemistry>In the formula, R is as defined above. In one embodiment, the reactant and aqueous medium are selected such that the phosphonium sulfonic acid salt precipitates from the aqueous medium.

In this embodiment, expression scan of (1) can be prepared in a one-step process sulfonic acid phosphonium salt, a sulfonyl in an aqueous medium in a single vessel fluoride (4) tetrasubstituted phosphonium hydroxide (5) Reaction Just let me do it. For example, the compound (4) may be dispersed or dissolved in the above-mentioned aqueous medium containing the co-solvent or the aqueous medium containing substantially no co-solvent, and then the tetrasubstituted phosphonium hydroxide (5) may be added. The order of addition does not seem to be important. For example, the reaction can also be achieved by dissolving the tetrasubstituted phosphonium hydroxide (5) in an aqueous medium and then adding the sulfonyl fluoride (4), or by simultaneously dissolving / dispersing the reactants and mixing. Combinations of different sulfonyl fluorides (4) and / or different tetrasubstituted phosphonium hydroxides (5) may be reacted.

As mentioned above, a wide range of reaction times, temperatures and other process conditions can be used, but room temperature is preferred for ease of manufacture. Generally, tetrasubstituted phosphonium hydroxide (5) is used in an amount of about 2 mol or more per mole of sulfonyl fluoride (4). More specifically, the molar ratio of the compound of formula (4) to the phosphonium hydroxide of formula (5) is about 1: 2.01 to about 1: 3, specifically about 1: 2.1 to about 1: 2.7. More specifically, it is about 1: 2.2 to about 1: 2.6. Optimal ratios may vary depending on the particular reactant, temperature, co-solvent (if present) and time, but can be readily determined by one of ordinary skill in the art.

In another embodiment, the method for producing a sulfonic acid phosphonium salt of the formula (1), the sulfonylfluoride of the formula (4), the tetrasubstituted phosphonium halide of the formula (3) and an alkali metal or alkaline soil in an aqueous medium. A method comprising a step of mixing with a metal base and a step of separating the phosphonium sulfonate of the formula (1) from the aqueous medium is provided. Suitable bases include alkaline hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide and magnesium hydroxide. Mixtures may also be used. Potassium hydroxide, sodium hydroxide and / or lithium hydroxide are preferred. In one embodiment, the reactant and aqueous medium are selected such that the phosphonium sulfonic acid salt precipitates from the aqueous medium.

Again, the order of addition does not seem to be important. The components may be mixed at the same time, or tetra-substituted phosphonium halide (3) is added to the aqueous solution / dispersion of the base and this medium / dispersion is added to the solution / dispersion of the sulfonyl fluoride (4). You may. In yet another embodiment, the sulfonyl fluoride (4) and the base are mixed and reacted for a period of time effective to produce the sulfonic acid alkali salt (2). The phosphonium halide (3) is then added to the medium to produce the product without isolating the sulfonic acid alkali salt (2). This method is simple and efficient and requires minimal time and material. Alternatively, the sulfonic acid alkali salt (2) may be isolated, redissolved with or without a co-solvent, and then added to the phosphonium halide (3).

A wide range of reaction times, temperatures and other process conditions can be used, but are preferably from about 25 ° C (room temperature) to about 100 ° C for ease of manufacture. The optimum reactant ratio can be easily determined by those skilled in the art, for example as described above.

The sulfonic acid phosphonium salt that can be produced by the method described in the present specification includes the following general formula (6).

<chemistry num="12"><img file="JP4932702B2_D0012.tif" /></chemistry>In the formula, F is fluorine, n is an integer from 0 to about 7, S is sulfur, and each R is the same or different aliphatic hydrocarbon group with 1 to about 18 carbon atoms or 6 carbon atoms. ~ About 18 aromatic hydrocarbon groups. In one embodiment, the three R groups in the organic phosphonium cation are the same aliphatic hydrocarbon group with 1 to about 8 carbon atoms or the same aromatic hydrocarbon group with 6 to about 12 carbon atoms. The fourth R group is a hydrocarbon group having 1 to about 18 carbon atoms. The antistatic composition containing phosphonium fluorinated sulfonate of the formula (6) as a main component utilizes its antistatic properties, compatibility and heat resistance (for example, imparting such antistatic properties to a thermoplastic resin). It can be used for a wide variety of purposes. Suitable thermoplastic resins include, but are not limited to, polycarbonate, polyetherimide, polyester, polyphenylene ether / polystyrene blends, polyamides, polyketones, acrylonitrile-butadiene-styrene (ABS), or one or more of the polymers described above. Combinations can be mentioned. Since the sulfonic acid phosphonium salt is a semi-solid substance having a low melting point, it can be treated as a molten liquid as it is. Some embodiments of the present invention are crystalline materials that are solid at room temperature (about 15 to about 25 ° C.) and are easy to weigh, handle and add to the thermoplastics described above.

In addition to the thermoplastic resin, the thermoplastic resin composition may contain various additives usually blended in this type of resin composition. A mixture of additives can also be used. Such additives can be mixed at the appropriate time in mixing the components to form the composition. Examples of suitable additives are impact resistance improvers, fillers, heat stabilizers, antioxidants, light stabilizers, plasticizers, mold release agents, UV absorbers, lubricants, pigments, dyes, colorants, foams. Agents, anti-drip agents and flame retardants.

The usual practice is to add an antistatic agent directly to the thermoplastic and mix it during polymer production or processing. It can be processed by conventional means such as extrusion, injection molding, compression molding or casting. The thermoplastic resin composition can be produced by a method generally available in the art, for example, in one embodiment, first a powdered thermoplastic resin, an antistatic agent and / or other optional component, as appropriate, chopped glass strands or the like. Blend with the filler in a Henchel high speed mixer. This blending is not particularly limited, but can be achieved by other low shear methods such as hand mixing. The blend is then fed through the hopper to the throat of the twin-screw extruder. Alternatively, one or more components may be fed directly to the extruder from the throat and / or downstream side stuffers and blended into the composition. Such additives may be compounded with the desired polymer resin into a masterbatch and supplied to the extruder. Extruders are generally operated at temperatures higher than those required to flow the composition. The extruded product is immediately quenched in a water bath and pelletized. Pellets produced by cutting the extruded product can have a length of 1/4 inch or less, if desired. Such pellets can be used for molding, shaping and shaping in the subsequent stage.

The amount of the sulfonic acid phosphonium salt added to the thermoplastic resin is an effective amount for reducing or eliminating the electrostatic charge, and can vary within a certain range. It has been found that if too little of the antistatic substituted sulfonic acid phosphonium salt is added to the resin, the tendency of static charge accumulation in articles made from the resin can persist. If too much antistatic additive is added, such an amount of addition is uneconomical and at some level may begin to adversely affect other properties of the resin. The thermoplastic resin with improved antistatic properties is about 0.01 to about 10% by weight (wt%), specifically about 0.2 to about 2.0 wt%, more specifically, based on the total weight of the antistatic agent and the polymer. With about 0.5 to about 1.5 wt% antistatic agent and about 90 to about 99.99 wt%, specifically about 99 to about 99.8 wt%, more specifically about 98.5 to about 99.5 wt% polymer. Obtained by use. In one embodiment, the antistatic agent is generally about 0.01 to about 3.0% by weight (wt%), specifically about 0.01 to about 3.0% by weight (wt%), with respect to the molding composition, in order to obtain favorable results using such internal application methods for clear polycarbonate grades. Is used in an amount of about 0.1 to about 1.5 wt%, more specifically about 0.4 to about 0.8 wt%. The antistatic agent provided in the present invention has stronger heat resistance than ordinary ionic surfactants (for example, phosphonium alkylsulfonate), and the amount added can be reduced. Moreover, the resin composition has good transparency and mechanical properties.

These phosphonium salts can also be used in the production of thermoplastic polymer compositions with improved thermal stability. In one embodiment, the polycarbonate composition containing the antistatic agent produced by any of the methods described above has a yellowness of less than about 15, specifically less than about 10, after aging at 130 ° C. for 936 hours. More specifically, it is less than about 8, and more specifically, it is less than about 6.

Thermoplastic resin compositions containing antistatic agents can be used, for example, in computer and office equipment housings such as monitor housings, handheld electronics housings such as mobile phone housings, electrical connectors, and lighting fixture components, ornaments. It can be used in the manufacture of articles such as household appliances, roofs, greenhouses, solariums, swimming pool enclosures, carrier tapes for semiconductor packaging materials, and auto parts.

The thermoplastic resin composition can be secondary processed into products by processes such as film and sheet extrusion, injection molding, gas assisted injection molding, extrusion molding, compression molding and blow molding. The film and sheet extrusion method is not particularly limited, and examples thereof include melt casting, inflated film extrusion, and calendering. Composite multilayer films or sheets can also be formed using coextrusion and lamination methods. A single-layer or multi-layer coating may be further provided on the single-layer or multi-layer substrate to impart additional properties such as scratch resistance, UV resistance, and aesthetics. The coating can be applied by conventional coating techniques such as roll coating, spray coating, dipping, brush coating or flow coating. Alternatively, the film and sheet can also be produced by casting a solution or suspension of a thermoplastic resin composition in a suitable solvent onto a substrate, belt or roll and then removing the solvent.

The oriented film can be produced by the inflation method or by stretching the cast or calendar film near the thermal deformation temperature using conventional stretching techniques. For example, a radial stretching pantograph can be used for multi-axis simultaneous stretching, or simultaneous or sequential stretching can be performed in the plane xy direction using a xy direction stretching pantograph. Also, uniaxial and biaxial stretching shall be achieved using a device having sequential uniaxial stretching sections, for example a machine equipped with roll sections having different velocities for stretching in the longitudinal direction and a tenter frame section for stretching in the transverse direction. You can also.

The thermoplastic resin composition of the present invention may be a multilayer sheet having a first sheet and a second sheet, and the first sheet is composed of a thermoplastic polymer having a first surface and a second surface, and the first sheet is formed. The first surface of the sheet is arranged on the first surface of a plurality of ribs, the second sheet is made of a thermoplastic polymer having the first surface and the second surface, and the first surface of the second sheet is the above-mentioned plurality. Place it on the second surface opposite the first surface of the rib.

The above-mentioned films and sheets can be further thermoplasticly processed into molded products by shaping and secondary molding processes such as thermoforming, vacuum forming, pressure molding, injection molding and compression molding. A multi-layer molded product can also be molded by injection molding a thermoplastic resin onto a single-layer or multilayer film or sheet substrate, and one or more colors are appropriately applied to the surface using, for example, screen printing or a transfer dye. Prepare a single-layer or multi-layer thermoplastic resin base material, shape and trim the base material into a three-dimensional shape to match the base material with the three-dimensional shape of the mold, and obtain a surface that matches the three-dimensional shape of the base material. The base material is fitted into the mold to be held, and the thermoplastic resin is injected into the mold cavity behind the base material to either (i) manufacture a permanently bonded integral three-dimensional product, or (ii) from the printed base material. The pattern or aesthetic effect may be transferred to the injection molding resin, the printing substrate may be taken out, and the aesthetic effect may be imparted to the molding resin.

Although it will be obvious to those skilled in the art, the above-mentioned articles are further limited to general curing including thermosetting, texture processing, embossing, corona treatment, flame treatment, plasma treatment and / or vacuum deposition. And the surface modification treatment may be applied to change the surface appearance to give the article an additional function.

Therefore, another embodiment of the present invention relates to articles, sheets and films made from the above thermoplastic resin compositions.

The above method can be used to rapidly produce the phosphonium salt (1) in high purity. In one embodiment, the total amount of ionic impurities is less than about 650 ppm, more specifically less than about 500 ppm, more specifically less than about 100 ppm, more specifically less than about 50 ppm, most specifically less than about 10 ppm. Is. In another embodiment, the alkali metal contained in the product is less than about 5 ppm, preferably less than about 4 ppm. In another embodiment, the halide contained in the product is less than about 500 ppm, preferably less than about 100 ppm, more preferably less than about 50 ppm, most preferably less than about 10 ppm. Other ionic contaminants (eg, phosphate or sulfate) are individually present in an amount of less than about 100 ppm, preferably less than about 50 ppm, most preferably less than about 10 ppm.

The method is further illustrated in the following non-limiting examples.

Differential scanning calorimetry (DSC) was performed by scanning the sample from 50 ° C to 100 ° C at a scanning rate of 10 ° C / min. Thermogravimetric analysis (TGA) was performed by scanning the sample from 50 ° C to 600 ° C at a scanning rate of 10 ° C / min. The ion content of the salt was measured by ion chromatography. Yellowness (YI) was measured with Gretag McBeth color-eye 7000A using propalette software.

In the following examples, "MQ water" refers to water that has been deionized and treated with a MilliQ® device. (MilliQ® is a trademark of Millipore Corporation.) "TBPBr" refers to tetrabutylphosphonium bromide.

<u style="single">Example 1</u> First, 5.00 g (MW302, 16.55 mmol) of perfluorobutane sulfonyl fluoride (A) is weighed into a 100 mL round-bottomed flask, stirred with a magnetic stir bar, and refluxed in an oil bath at 85 ° C. To do.

Next, 0.95 g (24.83 mmol) of lithium hydroxide (LiOH) is added to 25 mL of MQ water to dissolve and slowly add to A. The undissolved residue is then filtered off, collected in another 100 mL round bottom flask and reheated in an oil bath at 85 ° C. Next, 8.43 g (24.83 mmol) of TBPBr is dissolved in 25 mL of MQ water and slowly added to the filtrate to produce an antistatic product. After adding all dissolved TBPBr, the mixture is stirred for an additional 15 minutes. The mixture is then cooled (preferably in an ice / water bath) and then the water is decanted. Next, add 100 mL of MQ water and stir for 15 minutes while heating in an oil bath at 85 ° C. The mixture is then cooled to room temperature and the product is isolated by filtration and flushed with 25 mL of MQ water. The product is dried in a vacuum dryer at 50 ° C. The theoretical yield was 9.24 g of antistatic agent, and 3.8 g was obtained.

<u style="single">Example 2</u> First, 54.8 g (180.837 mmol) of lithium perfluorobutanesulfonate (Li Rimar) was added to 300 mL of room temperature MQ water to dissolve it, and 60.8 g (179.062 mmol) of TBPBr was added to 200 mL of room temperature MQ water. Add and dissolve. Filtration of the TBPBr solution and then gradual pouring into the Li Rimar salt solution with stirring with a propeller stirrer produces antistatic agent products. After adding all TBPBr, the reaction mixture is stirred for an additional 15 minutes. After completion of the reaction, the antistatic product is isolated by filtration and flushed with 50 mL of MQ water to remove most impurities. In addition, the antistatic product is suspended in MQ water, heated to 80 ° C., stirred for a few minutes, the mixture is cooled and the antistatic product is recrystallized for additional purification. The antistatic agent product can then be isolated by filtration and dried in a vacuum dryer at 50 ° C. The theoretical yield was 100.0 g of antistatic agent, and 87.1 g was obtained.

<u style="single">Example 3</u> First, 5.00 g (MW302, 16.55 mmol) of perfluorobutane sulfonyl fluoride (A) is weighed into a 100 mL round-bottomed flask, stirred with a magnetic stir bar, and refluxed in an oil bath at 85 ° C. To do.

Next, add 2.4 times the amount of A (39.72 mmol) of 32 wt% NaOH solution slowly. This amount corresponds to 1.58 g NaOH (4.94 g 32 wt% solution). The mixture is then refluxed for 1 hour, then 50 mL of MQ water is added and stirred until everything is dissolved. Next, 5.62 g (16.55 mmol) of TBPBr is dissolved in 25 mL of MQ water and slowly added to this solution to produce an antistatic product. After adding all dissolved TBPBr, the mixture is stirred for an additional 15 minutes. The mixture is then cooled (preferably in an ice / water bath) and then the water is decanted. Then 100 mL of MQ water is added and stirred for 15 minutes while heating in an oil bath at 85 ° C. The mixture is cooled to room temperature and the antistatic product is isolated by filtration and flushed with 25 mL of MQ water. The antistatic product is then dried in a vacuum dryer at 50 ° C. The theoretical yield was 9.24 g of antistatic agent, and 5.8 g was obtained.

<u style="single">Example 4</u> First, 5.77 g (18.083 mmol) of sodium perfluorobutanesulfonate (Na Rimar) was added to 50 mL of room temperature MQ water to dissolve it, and 6.08 g (17.906 mmol) of TBPBr was added to 20 mL of room temperature MQ water. Add and dissolve. Filtration of the TBPBr solution and then gradual pouring into the Na Rimar salt solution with stirring with a strong magnetic stir bar produces an antistatic agent product. After adding all TBPBr, the reaction mixture is stirred for an additional 15 minutes. After completion of the reaction, the antistatic product is isolated by filtration and flushed with 50 mL of MQ water to remove most impurities. In addition, the antistatic product is stirred in MQ water, heated to 80 ° C., stirred for a few minutes, the mixture is cooled to crystallize the antistatic product and additional purification is performed. The antistatic product is then isolated by filtration and dried in a vacuum oven at 50 ° C. The theoretical yield was 10.0 g of antistatic agent, and 8.10 g was obtained.

<u style="single">Example 5</u> First, 5.00 g (MW302, 16.55 mmol) of perfluorobutane sulfonyl fluoride (A) is weighed into a 100 mL round-bottomed flask, stirred with a magnetic stir bar, and refluxed in an oil bath at 85 ° C. To do. Next, 4.46 g of 50 wt% KOH solution is slowly added to provide 2.4 equivalents of KOH (2.23 g, 39.72 mmol) (4.46 g of 50 wt% solution). Reflux the mixture for 1 hour, then add 75 mL of ethanol / MQ water (3/4 by volume) and stir until everything is dissolved. Next, 5.56 g (16.38 mmol) of TBPBr is dissolved in 25 mL of MQ water and slowly added to this solution to produce an antistatic product. After adding all the dissolved TBPBr, the mixture is stirred for an additional 15 minutes and then the mixture is cooled to room temperature. Extract the antistatic product with 75 mL of dichloromethane in a separatory funnel and wash 3 times with 50 mL of MQ water. Remove the organic layer under reduced pressure (50 ° C, P_start= 475mbar and P_end= 125mbar). In addition, the antistatic product can be agitated in MQ water, heated to 80 ° C, agitated for a few minutes, the mixture cooled to crystallize the antistatic product for additional purification. it can. The antistatic product is then isolated by filtration and dried in a vacuum oven at 50 ° C. The theoretical yield was 9.24 g of antistatic agent, and 6.04 g was obtained.

<u style="single">Comparative example 6</u> First, 6.06 g (17.9 mmol) of potassium perfluorobutanesulfonate (K Rimar) was added to 75 mL of an ethanol / MQ aqueous solution (3/4 by volume) to dissolve it, and 6.01 g (17.7 mmol) of TBPBr was added. Dissolve by adding to 25 mL of MQ water at room temperature. Gradually pouring the TBPBr solution into the K Rimar salt solution with agitation produces an antistatic product. After adding all TBPBr, the reaction mixture is stirred for an additional 15 minutes. Extract the antistatic product with 75 mL of dichloromethane in a separatory funnel and wash 3 times with 50 mL of MQ water. Remove the organic layer under reduced pressure (50 ° C, P_start= 475mbar and P_end= 125mbar). In addition, the antistatic product can be agitated in MQ water, heated to 80 ° C, agitated for a few minutes, the mixture cooled to crystallize the antistatic product for additional purification. it can. The antistatic product is then isolated by filtration and dried in a vacuum oven at 50 ° C. The theoretical yield was 10.0 g of antistatic agent, and 8.91 g was obtained.

<u style="single">Example 7</u> First, 5.00 g (MW302, 16.55 mmol) of A is weighed into a 100 mL two-necked round-bottom flask, stirred with a magnetic stirrer, and refluxed in an oil bath at 85 ° C. Next, 10.98 g (39.72 mmol) of 40% tetrabutylphosphonium hydroxide is added. The mixture is then refluxed for 1 hour. Then 50 mL of MQ water is added and stirred for an additional 15 minutes. The mixture is then cooled (preferably in an ice / water bath) and then the water is decanted. Then 100 mL of MQ water is added and stirred for 15 minutes while heating in an oil bath at 85 ° C. The mixture is then cooled to room temperature and the antistatic product is isolated by filtration and flushed with 25 mL of MQ water. The antistatic product is then dried in a vacuum dryer at 50 ° C. The theoretical yield was 9.24 g of antistatic agent, and 7.4 g was obtained.

Table 1 shows the characteristics of antistatic agents produced by the various synthetic routes detailed in Examples 1-7 above. The reference sample is a perfluorobutanesulfonic acid antistatic agent marketed by DuPont under the trade name Zonyl® FASP-1. The melting point is measured using differential scanning calorimetry (DSC). The thermal decomposition of antistatic agents is measured by thermogravimetric analysis (TGA) and is expressed as the temperature at which the decomposition is first detected.

<tables num="1"><img file="JP4932702B2_D0013.tif" /></tables> As is clear from Table 1, the process of Example 3 is particularly advantageous in terms of high yield. In addition, the synthesis step is simple.

Table 2 shows that the antistatic agents produced by the various synthetic pathways detailed in Examples 1-2 above contain low ionic impurities after washing with water at 80 ° C.

<tables num="2"><img file="JP4932702B2_D0014.tif" /></tables> As is known, certain by-products commonly found in antistatic agents can be detrimental to the nature of the thermoplastic polymer (eg, polycarbonate) in which it is blended. For example, as shown in Figure 1, increased bromine abundance can result in increased yellowing of polycarbonate after 936 hours of heat aging at 130 ° C. Table 3 further shows the change in YI (ΔYI) after heat aging of polycarbonate containing the indicated amount of ionic contaminants. Spots were found on the heat-aged polycarbonate, probably due to potassium and sodium contamination.

<tables num="3"><img file="JP4932702B2_D0015.tif" /></tables> In order to judge the cleaning effectiveness of the antistatic agent of the above example, 10.02 g of the uncleaned antistatic agent produced in Example 2 is weighed in a 150 mL beaker and charged, and 100 mL of MQ water is added. Stir this to evenly disperse the antistatic agent in water and continue stirring at room temperature for 15 minutes. The antistatic agent is then filtered, dried and tested for ionic impurities.

In the second test, 10.06 g of the unwashed antistatic agent produced in Example 2 above is weighed and charged in a 150 mL beaker, and 100 mL of MQ water is added thereto. Stir this well to evenly disperse the antistatic agent in water and continue stirring at 80 ° C for 15 minutes. At that temperature, the antistatic agent of Example 2 melts, producing an emulsion during stirring. The mixture is then cooled, the solid is filtered, dried and tested for ionic impurities. Table 4 shows the yield after washing, and Table 5 shows the result of ion chromatography.

<tables num="4"><img file="JP4932702B2_D0016.tif" /></tables>

<tables num="5"><img file="JP4932702B2_D0017.tif" /></tables> It is possible to synthesize antistatic agents according to all of the above examples. Any ionic impurities can be easily removed by washing the antistatic agent with water at room temperature or 80 ° C.

Even if it is described in the singular form, it means including multiple cases unless it is clear from the context. As used herein, terms such as "first" and "second" do not represent any order, quantity or importance, but rather are used to distinguish one component from another. The end points of all ranges that represent the same property are combinable and include the expressed end points. The modifier "about" used with respect to a quantity includes the stated value and has a contextual meaning (including, for example, the degree of error associated with the measurement of a particular quantity).

Although typical embodiments have been described above for the purpose of illustration, the above description should not be construed as limiting the technical scope of the present invention. Therefore, those skilled in the art will be able to recall various modifications, adaptations and alternatives without departing from the technical ideas and scope of the invention.

<figref num="1">It is a graph which shows that the presence of an increasing amount of bromine results in an increase in yellowing of polycarbonate after 936 hours of heat aging at 130 ° C.</figref>