Copolymer having cationic group

Abstract

To provide a new polymer capable of providing a resin product having functionality.SOLUTION: There are provided: a copolymer comprising an acrylonitrile monomer unit and a styrene monomer unit, which is a copolymer having a cationic group at the end, in which the cationic group is a residue of 2,2'-azobis-(2-(1,3-dimethyl-4,5-dihydro-1H-imidazol-3-ium-2-yl))propane triflate; an additive for imparting antimicrobial properties to a resin which comprises the copolymer; a resin composition comprising the copolymer and a general-purpose resin such as ABS resin; and a resin molded body obtained by molding the resin composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to copolymers having cationic groups. [Background technology]

[0002] Resins are lightweight and durable materials that are used in a wide range of products, including food packaging, medical devices, and household goods. Resin products have a variety of properties depending on the polymer used. For example, Patent Document 1 discloses a polymer having a cationic group at its terminal, which is produced using a cationic radical polymerization initiator, and an antimicrobial resin molded article containing this polymer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2019 / 208674 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a novel polymer that can be used to provide functional resin products, and also to provide a polymer that can be used as an additive for versatile resins such as ABS resin. [Means for solving the problem]

[0005] The present inventors have succeeded in producing a novel copolymer having a cationic group by using the cationic radical polymerization initiator described in Patent Document 1. They have also found that this copolymer has excellent properties as an additive for general-purpose resins, and have completed the present invention based on this finding.

[0006] As some of the representative aspects of the present invention, the present disclosure provides the following [1] to

[10] . [1] A copolymer comprising acrylonitrile monomer units and styrene monomer units, having a cationic group at the end, a copolymer, wherein the cationic group is a residue of a polymerization initiator represented by the following formula (I): [ka] In the formula, X f - is the counter anion.

[0007] [2] The copolymer according to [1], wherein the residue is represented by the following formula: [ka]

[0008] [3] The copolymer according to [1] or [2], wherein the molar ratio of the acrylonitrile monomer units to the styrene monomer units is 9:1 to 1:99. [4] The copolymer according to any one of [1] to [3], which has a number average molecular weight of 5,000 to 100,000. [5] A resin composition comprising the copolymer according to any one of [1] to [4]. [6] The resin composition according to [5], which contains a polymer containing a butadiene monomer unit. [7] The resin composition according to [5] or [6], which contains an acrylonitrile-butadiene-styrene resin. [8] A resin molded article obtained by molding the resin composition according to any one of [5] to [7]. [9] An additive for imparting antimicrobial properties to a resin, comprising the copolymer according to any one of [1] to [4].

[10] The additive according to [9], wherein the resin is an acrylonitrile-butadiene-styrene resin. [Effects of the Invention]

[0009] The present disclosure provides a novel copolymer having a cationic group. The copolymer of the present disclosure can provide a functional resin product. Because this copolymer has high kneadability with general-purpose resins, it can also be used as a resin additive. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows a comparison of the FT-IR spectrum (top) of the copolymer (ADIP-AS) prepared in the examples with the FT-IR spectra of other polymers (poly(styrene:acrylonitrile) (styrene 77 mol%); polyacrylonitrile; polystyrene) obtained from an FT-IR library. [Figure 2] 1 shows the appearance of a sheet in which the copolymers (ADIP-AS and ADIP-PS) prepared in the examples were kneaded with ABS resin. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Note that the embodiments shown below are described for illustrative purposes only, and the following description of the present embodiments should not be construed as limiting the scope of the claims. In the following description, the amount of a substance, such as the content, is expressed by mass unless otherwise specified. Furthermore, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0012] <Copolymer having cationic groups> The copolymers of the present disclosure include acrylonitrile monomer units, styrene monomer units, and cationic groups. The cationic group in the copolymer of the present disclosure is a residue of a cationic radical polymerization initiator represented by formula (I):

[0013] [ka] In the formula, X f - is the counter anion.

[0014] The compound represented by formula (I) has an azo group and decomposes under heat or light to generate carbon radicals, which act on a monomer having a vinyl group, causing a radical polymerization reaction. After the polymerization reaction, one end of the polymer has the following group (* indicates the bonding position) as a residue of the polymerization initiator. Therefore, the copolymer of the present disclosure has a positive charge at one end.

[0015] [ka]

[0016] X in formula (I) f - The "counter anion" as used herein is not particularly limited as long as it is an anion commonly used as a counter anion of an organic compound in the technical field of organic chemistry, and includes, for example, halide anions (chloride ion, bromide ion, fluoride ion, iodide ion), conjugate bases of organic acids (e.g., acetate ion, trifluoroacetate ion), nitrate ion, sulfate ion, carbonate ion, etc. Preferred counter anions in the present disclosure include, for example, trifluoromethanesulfonate ion (triflate), chloride ion, nitrate ion, etc. Of these, trifluoromethanesulfonate ion is preferred. The copolymer of the present disclosure may be a copolymer salt formed with an anion. In this case, the anion may be a counter anion (X f - ) are listed.

[0017] The cationic radical polymerization initiator represented by formula (I) can be produced, for example, by the method described in WO 2017 / 043484 or JP 2017-051113 A, the contents of which are incorporated herein by reference.

[0018] In this specification, an "acrylonitrile monomer unit" is a structural unit in a copolymer that is derived from acrylonitrile, and a "styrene monomer unit" is a structural unit in a copolymer that is derived from styrene. In the copolymer of the present disclosure, the molar ratio of acrylonitrile monomer units to styrene monomer units is not particularly limited. The "molar amount of acrylonitrile monomer units:molar amount of styrene monomer units" may be, for example, 9:1 to 1:99, preferably 2:1 to 1:99, and more preferably 1:1 to 1:9. For example, high antimicrobial activity can be obtained in the range of 1:3 to 1:8. The molar ratio of acrylonitrile monomer units to styrene monomer units in the copolymer is 1 It can be determined by H-NMR measurement. Specifically, it can be determined from the ratio of the signal integral value of the methylene protons and methine protons of both the acrylonitrile monomer and the styrene monomer components to the signal integral value of the phenyl proton of the styrene monomer.

[0019] The copolymer of the present disclosure may contain repeating units other than acrylonitrile monomer units and styrene monomer units. Examples of such repeating units include repeating units derived from butadiene. In the copolymer of the present disclosure, the total of the acrylonitrile monomer units and styrene monomer units is preferably 90 mol% or more of all repeating units, more preferably 95 mol% or more, even more preferably 98 mol% or more, and particularly preferably 99 mol% or more. There is no particular upper limit to the total content, and all of the monomer-derived structural units may be acrylonitrile monomer units or styrene monomer units.

[0020] The order of bonding of multiple types of monomer units in the copolymer of the present disclosure is not particularly limited. The copolymer of the present disclosure may be an alternating copolymer, a random copolymer, or a block copolymer, but is preferably an alternating copolymer or a random copolymer. The copolymer of the present disclosure may have a crosslinked structure, but preferably contains at least a linear structure, and more preferably has a linear structure.

[0021] The molecular weight of the copolymer of the present disclosure is not particularly limited. For example, the weight-average molecular weight may be 5,000 to 1,000,000 or 8,000 to 900,000, and the number-average molecular weight may be 3,000 to 200,000, preferably 4,000 to 150,000. Furthermore, when used as a component in a resin composition or as a resin additive having antimicrobial activity, the copolymer of the present disclosure preferably has a weight-average molecular weight of 80,000 to 800,000, more preferably 100,000 to 600,000, and even more preferably 120,000 to 400,000. Furthermore, the number-average molecular weight is preferably 5,000 to 100,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel filtration chromatography and are defined as polystyrene equivalent values. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by Tosoh Corporation) and a Shodex GPC KF-405L HQ (manufactured by Showa Denko K.K.) column. Chloroform can be used as the eluent, and a 254 nm UV (ultraviolet) detector can be used for detection.

[0022] The copolymer of the present disclosure can be synthesized based on common knowledge in the technical field of polymer synthesis. Specifically, it can be obtained by carrying out the radical polymerization reaction as described above using at least acrylonitrile and styrene as monomers. In this polymerization reaction, a cationic radical polymerization initiator represented by formula (I) is used as the polymerization initiator.

[0023] The amount of the polymerization initiator used can be selected appropriately within the range of concentration at which the radical polymerization reaction proceeds. For example, the polymerization initiator can be used in an amount of 0.5 mol % or more, preferably 1 mol % or more, based on the total amount of the monomers used. In another embodiment, the amount of the polymerization initiator used is not particularly limited as long as a copolymer of the present disclosure is obtained, but is preferably 3% by mass or more, more preferably 3 to 9% by mass, even more preferably 4 to 8% by mass, and particularly preferably 5 to 7% by mass, based on the total amount of the monomers used. The reaction solvent used in the polymerization reaction is not particularly limited, but examples include water, toluene, benzyl alcohol, dioxane, dimethylformamide, dimethyl sulfoxide, isopropanol, or a mixture of two or more of these solvents. Water containing a surfactant (e.g., sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium pentadecane sulfate, N-dodecyl-N,N,N-trimethylammonium bromide, N-cetyl-N,N,N-trimethylammonium bromide, Triton X-100, etc.) may also be used.

[0024] The polymerization reaction conditions are not particularly limited, but examples include a reaction temperature of 0 to 100°C, preferably 50 to 70°C, and a reaction time of 1 to 48 hours, preferably 2 to 16 hours. Furthermore, based on common knowledge in the technical field of polymer synthesis, the polymerization reaction can also be induced by ultraviolet irradiation, if necessary. For the production of the copolymer of the present disclosure, reference may be made to the method described in WO 2017 / 043484, the contents of which are incorporated herein by reference.

[0025] <Resin composition> The copolymer of the present disclosure may be provided as a resin composition containing the copolymer of the present disclosure. The resin composition may further contain a resin (e.g., a polymer other than the copolymer of the present disclosure). In this case, the copolymer of the present disclosure is preferably contained in the resin composition as an additive for imparting antimicrobial properties, as described below. Examples of the resin include thermoplastic resins, thermosetting resins, polymer rubbers, etc., and thermoplastic resins are preferred. The resin may or may not have a polar group such as a cationic group.

[0026] Specific examples of resins include polymers containing butadiene monomer units, acrylonitrile-styrene (AS) resins (excluding those corresponding to the copolymers of the present disclosure), acrylonitrile-butadiene-styrene (ABS) resins, acrylonitrile-ethylene-propylene rubber-reinforced styrene (AES) resins, acrylonitrile-polyacrylate rubber-reinforced styrene (AAS) resins, methyl methacrylate-styrene (MS) resins, methyl methacrylate-butadiene-styrene (MBS) resins, and high-impact polystyrene. Of these, AS resins or ABS resins are preferred, and ABS resins are more preferred. The composition ratio of the monomer units in the copolymer resin is not particularly limited.

[0027] The amount of the copolymer of the present disclosure in the resin composition may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 45% by mass or more relative to the total amount of the copolymer of the present disclosure and resins other than the copolymer of the present disclosure, and may be 100% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 55% by mass or less. The range of the content may be any combination of the above lower and upper limits, and is preferably 1% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less, even more preferably 40% by mass or more and 100% by mass or less, and particularly preferably 50% by mass or more and 90% by mass or less.

[0028] Depending on the application, various known additives such as fillers, plasticizers, leveling agents, release agents, thickeners, viscosity reducers, stabilizers, antioxidants, ultraviolet absorbers, inorganic pigments, organic pigments, and carbon black can be blended into the resin composition according to known recipes.

[0029] The form of the resin composition is not particularly limited. For example, the resin composition may be a simple mixture of the copolymer of the present disclosure and other polymers in a powder or pellet form, or may be a melt-kneaded product of the copolymer of the present disclosure and other polymers. The melt-kneaded product may be, for example, in the form of pellets.

[0030] The resin composition may be a paint. The copolymer of the present disclosure may form polymer particles and be contained in the paint. The resin composition may also contain a solvent for water, oil, thinner, or alcohol. For details about the polymer particles and the paint, see International Publication No. 2019 / 208674, the contents of which are incorporated herein by reference.

[0031] <Resin molded body> The resin molded article can be produced by heating or cooling the copolymer of the present disclosure or the above-described resin composition as necessary and molding it in accordance with common technical knowledge widely known to those skilled in the art. The molding method is not particularly limited, but examples thereof include conventionally known melt molding methods such as a two-roll method, injection molding, extrusion molding, and compression molding. The molding temperature for forming the resin molded article may be within a temperature range that allows molding of the resin used, depending on the molding method and the type of resin used. The resin molded product may have any shape depending on the intended use, and examples of the shape include granules, pellets, fibers, films, sheets, containers, electrical appliances, and parts thereof.

[0032] The resin molded article may be composed solely of the copolymer of the present disclosure or a resin composition containing the copolymer of the present disclosure, or may have a multilayer structure in combination with other resins that do not contain the copolymer of the present disclosure.

[0033] Examples of product forms using resin molded bodies include, but are not limited to, building materials, various automobile components, toys, food storage containers, medical supplies (white coats, curtains, towels, mats, wallpaper, files, door handles, etc.), kitchen utensils (cutting boards, scrubbing brushes, sinks, washtubs, etc.), toiletries (toothbrushes, cups, combs, bath stools, toilet seats, etc.), stationery (ballpoint pens, writing pads, files, erasers, etc.), home appliances (refrigerators, washing machines, dryers, vacuum cleaners, telephones, kettles, etc.), and other daily necessities (shoe insoles, cards, belts, wallets, etc.).

[0034] <Uses of the copolymer of the present disclosure> The copolymer of the present disclosure can be used in various applications that utilize the functionality derived from the terminal cationic groups. In the examples described below, it is shown that a resin product containing the copolymer of the present disclosure has antimicrobial properties. As an example, the copolymer of the present disclosure can be used as an additive to impart antimicrobial properties to a resin. The resin used in this case is not particularly limited, but examples include the resins listed above, and ABS resin is preferred from the viewpoint of kneadability.

[0035] In the present disclosure, "antimicrobial" refers to the property of inhibiting the development, growth, and / or proliferation of microorganisms. Here, "microorganisms" refers to organisms that are classified as "microorganisms" in biological taxonomy, and is a concept that includes, for example, gram-positive bacteria such as Staphylococcus aureus, gram-negative bacteria such as Escherichia coli, fungi, yeast, viruses, etc. In a preferred embodiment of the present disclosure, "antimicrobial" refers to the property of inhibiting the development, growth, and / or proliferation of gram-positive bacteria such as Staphylococcus aureus and gram-negative bacteria such as Escherichia coli, i.e., antibacterial properties.

[0036] A resin composition containing the copolymer of the present disclosure can be used as an antimicrobial resin composition. In addition, the resin composition containing the copolymer of the present disclosure can be used as a raw material for producing paints and resin molded articles, and can be used to produce antimicrobial products.

[0037] Resin products may come into contact with various bacteria and microorganisms in daily life. Therefore, antimicrobial agents suitable for resin products have always been in demand. As a method of imparting antimicrobial performance to resins, a method of kneading silver as an additive has been used for a long time. While it is a highly versatile technique, it is said that there are problems with the potential adverse effects of silver particles released into the environment on the ecosystem and the sustainability of the antibacterial effect.

[0038] Without being bound by a specific theory, for example, in a resin molded body containing the copolymer of the present disclosure, it is considered that excellent antimicrobial action is exhibited because the positive charge of the copolymer of the present disclosure is exposed on the surface of the resin molded body. The fact that the positive charge is exposed on the surface of the resin molded body can be confirmed, for example, by the method using an anionic fluorescent dye described in ACS Omega 2024, 9, 9803-9812. Since the cationic group that brings about the above positive charge is covalently bonded to the end of the copolymer having a cationic group, it is chemically stable, does not elute a cationic compound that causes irritation, and has a high safety feature. In addition, since antimicrobial properties can be imparted by simply blending a very small amount of the copolymer having a cationic group, an antimicrobial resin molded body can be manufactured simply and at low cost.

Examples

[0039] Hereinafter, the present invention will be described in detail with reference to examples. The examples shown below are described for illustrative purposes, and the content of the present invention is not limited to the following examples at all.

[0040] <Synthesis of ADIP> The cationic radical polymerization initiator 2,2'-azobis-(2-(1,3-dimethyl-4,5-dihydro-1H-imidazol-3-ium-2-yl)) propane triflate (ADIP) represented by the formula (I) was synthesized according to the method described in International Publication No. 2017 / 043484 or JP-A-2017-051113.

[0041] <Synthesis Example 1: Synthesis of polyacrylonitrile-styrene copolymer (ADIP-AS) using ADIP> Two 350 mL baffled separable flasks (reaction vessels) were prepared, and 112.5 g (1.08 mol) of styrene and 19.1 g (0.36 mol) of acrylonitrile were dispensed into each. 75 g of toluene was dispensed into each reaction vessel. The reaction vessels were attached to a mantle heater, stirring was started at 150 rpm (using a 40 mm diameter, four-blade PTFE stirring rod), and Ar bubbling was performed for 10 minutes. 8.73 g (14.4 mmol) of ADIP was dissolved in 30.6 g of benzyl alcohol and added to each reaction solution. The mantle heater was set to 40°C and the mixture was heated. After 40 hours, the mixture was removed from the mantle heater and the reaction was stopped. The mixture was reprecipitated with 4.5 L of methanol. The reaction solutions in each reaction vessel were mixed and reprecipitation was carried out (the reaction solution was divided into two and each was reprecipitated by adding dropwise to 1.5 L of methanol while stirring. The precipitate was then added to another 1.5 L of methanol, and a total of 4.5 L of methanol was used for reprecipitation). The precipitate was spread on a metal tray and left in a draft for one day. It was then vacuum dried for three days. The yield was 147.95 g, a 52.7% yield. The molecular weight was measured by gel filtration chromatography, and the number average molecular weight was approximately 12,000 and the weight average molecular weight was approximately 130,000. Measured using a nuclear magnetic resonance spectrometer (Bruker AV-300N), 1 The molar ratio of acrylonitrile monomer units to styrene monomer units was calculated by H-NMR measurement, and it was found that acrylonitrile:styrene was 1.0:2.8.

[0042] <Synthesis Example 2: Synthesis of polyacrylonitrile-styrene copolymer (ADIP-AS) using ADIP> 10 g (96 mmol) of styrene, 1.7 g (32 mmol) of acrylonitrile, and 6 g of toluene were separately placed in a 30 mL vial (reaction vessel). The reaction vessel was stirred with a stirrer. 0.8 g (1.28 mmol) of ADIP dissolved in 2.8 g of benzyl alcohol was added. The reaction vessel was placed in a water bath heated to 40 °C and reacted with stirring. After 48 hours, it was removed from the water bath to stop the reaction. It was reprecipitated with 200 mL of methanol and vacuum dried for 2 days. The yield was 6.87 g and the yield rate was 51.2%. By 1 calculating the composition ratio of acrylonitrile monomer units and styrene monomer units by 1H-NMR measurement using a nuclear magnetic resonance apparatus (AV-300N manufactured by Bruker), acrylonitrile:styrene = 1.0:7.0 (molar ratio).

[0043] <Reference Synthesis Example 1: Synthesis of Polystyrene (ADIP-PS) Using ADIP> 1000 g (9.6 mol) of styrene and 500 g of toluene were separately placed in a reaction vessel. While rotating the stirring blade at 100 rpm, Ar bubbling was carried out at 100 mL / min. 58.2 g (0.096 mol) of ADIP dissolved in 204 g of benzyl alcohol was added to the reaction solution. It was heated with stirring at 40 °C for 48 hours to react. It was reprecipitated with 18 L of methanol and vacuum dried overnight. The yield was 557.02 g and the yield rate was 54.1%. When the molecular weight was measured by gel filtration chromatography, the number average molecular weight was about 23,000 and the weight average molecular weight was about 180,000. [[ID=lo]]

[0044] <Detection of Triflate Group by FT-IR> Using Fourier transform infrared spectroscopy (FT-IR), the characteristic functional groups of ADIP-AS obtained in Synthesis Example 1 were determined. A Nicolet IS50 FT-IR infrared spectrophotometer (Thermo Fisher Scientific, USA) equipped with an ATR attachment using a diamond crystal plate as a reflector and a deuterated triglycine sulfate (DTGS) detector was used. The absorbance was 500 - 4000 cm -1Measurements were taken by scanning 32 times within the specified range. The obtained spectrum is shown in Figure 1. In Figure 1, along with the spectrum of ADIP-AS (1), the spectra of poly(styrene:acrylonitrile) (77 mol% styrene) (2), polyacrylonitrile (3), and polystyrene (4), which were obtained from the FT-IR library (HR Hummel Polymer and Additives), are shown. From Figure 1, it can be seen that absorption is observed only in ADIP-AS synthesized using ADIP near 640 cm -1 This is a peak characteristic of triflate ions. The detection of counter ions confirmed the presence of cationic groups in the copolymer.

[0045] <Manufacture of sheets using ADIP-AS> The ADIP-AS (powder) obtained in Synthesis Example 1 was sandwiched between a polyimide sheet and a stainless steel (SUS) plate, and pressed using a hot press machine at 140 °C or 170 °C for about 20 seconds per press. The sheet cooled below the glass transition temperature was peeled off from the polyimide film, cut into four pieces, and then sandwiched again between the polyimide film and the SUS plate, and the same heating and pressing process was repeated 10 times.

[0046] <Manufacture of sheets using general-purpose polystyrene (PS)> ​​​​​​The ADIP-AS and general-purpose PS sheets were cut into circular sheets with a diameter of 5 cm each to confirm the presence of cationic groups on the surface. The surface adsorption of the anionic fluorescent dye, 6-(p-toluidino)-2-naphthalenesulfonic acid sodium salt (TNS), was measured. TNS was dissolved in ethanol to a concentration of 25 μM and then diluted 10-fold with water to obtain a 2.5 μM TNS solution. 16 μL of the 2.5 μM TNS solution was dropped onto each of the above sheets, and a 12 mm diameter circular glass cover was placed on top. The sample was left at room temperature for 1 minute, after which the cover glass was removed and 10 μL of the TNS solution was sampled. 90 μL of water and 400 μL of dioxane were added to the collected TNS solution, and the fluorescence intensity at the maximum fluorescence wavelength of 421 nm with 370 nm excitation was measured using a spectrofluorometer (FP-8500). The concentration was determined from the TNS calibration curve, and the adsorption rate was calculated. While 1.4% of TNS was adsorbed onto the general-purpose PS sheet used for comparison, 41.4% of TNS was adsorbed onto the ADIP-AS sheet. These results confirmed that cationic groups (positively charged) were exposed on the surface of the ADIP-AS sheet.

[0048] <Antibacterial test> The antimicrobial test of the sheet using ADIP-AS manufactured as described above was carried out in accordance with JIS Z 2801:2000, Antibacterial Products - Antibacterial Test Method. The bacterial species tested in the antimicrobial test was Staphylococcus aureus subsp. aureus NBRC 12732. The polyethylene film was cut into a 5 cm square and used as an untreated test piece. The results are shown in Table 1. The antibacterial activity values ​​calculated from the results shown in Table 1 according to the following formula are shown in Table 2. An antibacterial activity value of more than 2.0 is evaluated as having antibacterial properties. Antibacterial activity value = [Number of viable bacteria on polyethylene film after 24 hours ( / cm 2 ) - [the average of the logarithmic values ​​of the number of viable bacteria on the test film after 24 hours ( / cm 2 ) (average of logarithmic values)

[0049]

Table 1

[0050]

Table 2

[0051] According to Table 2, the antibacterial activity values of the sheets manufactured under any conditions exceeded 2.0, and high antibacterial properties were recognized.

[0052] <Manufacture of Sheets by Kneading ADIP-AS and General-Purpose ABS Resin> The powder of ADIP-AS obtained in Synthesis Example 1 and the pellets of ABS (black: ABS filament for 3D printer) were mixed at the following mass ratios. It was adjusted so that the total amount became 1 g. ADIP-AS:ABS = 9:1 ADIP-AS:ABS = 7:3 ADIP-AS:ABS = 1:1 The mixed polymer was sandwiched between a polyimide film and a stainless steel (SUS) plate and pressed at 140 °C for about 20 seconds per time. A hot press machine (MH-5P, manufactured by Masada Seisakusho) was used for pressing. The heated sheet was peeled off from the polyimide film, divided into four parts, and then sandwiched again between the polyimide film and the SUS plate, and the same heating and pressing process was repeated 8 times.

[0053] <Manufacture of Sheets by Kneading ADIP-PS and General-Purpose ABS Resin> The powder of ADIP-PS and the pellets of ABS (black) were mixed at the following mass ratios. It was adjusted so that the total amount became 1 g. ADIP-PS:ABS = 9:1 ADIP-PS:ABS = 7:3 ADIP-PS:ABS = 1:1 The mixed polymer was sandwiched between polyimide film and stainless steel (SUS) plates and pressed at 140°C for approximately 20 seconds each time. A heat press (MH-5P Masada Manufacturing) was used for pressing. The heated sheet was peeled off from the polyimide film, divided into four pieces, and then sandwiched again between polyimide film and SUS plates, and the same heat pressing process was repeated eight times.

[0054] <Evaluation of mixing degree> The manufactured sheet was imported into Image J and subjected to binarization to quantify the degree of kneading. After binarization, areas judged as black indicate that ABS resin or ABS resin has been kneaded with ADIP-AS or ADIP-PS, while areas judged as white indicate that only ADIP-AS or ADIP-PS has been kneaded, not kneaded. Figure 2 shows the appearance of the sheet, and Table 3 shows the proportion of black and white areas after binarization.

[0055] [Table 3]

[0056] A significant difference was observed in the degree of mixing with ABS resin between ADIP-PS and ADIP-AS. This difference was particularly evident in samples with a low ABS ratio. ADIP-AS was considered to be a polymer that was easier to mix with ABS than ADIP-PS. Furthermore, when compared with ABS resins kneaded at the same ratio, the ABS resin kneaded with ADIP-AS was stronger than the ABS resin kneaded with ADIP-PS.

Claims

1. A copolymer comprising acrylonitrile and styrene monomer units, It has a cationic group at the end, a copolymer, wherein the cationic group is a residue of a polymerization initiator represented by the following formula (I): 【Chemical 1】 In the formula, X f - is the counter anion.

2. 2. The copolymer of claim 1, wherein the residue is represented by the formula: 【Chemistry 2】

3. 2. The copolymer of claim 1, wherein the molar ratio of said acrylonitrile monomer units to said styrene monomer units is from 9:1 to 1:

99.

4. The copolymer of claim 1 having a number average molecular weight of 5,000 to 100,000.

5. A resin composition comprising the copolymer according to any one of claims 1 to 4.

6. The resin composition of claim 5 , comprising a polymer containing butadiene monomer units.

7. The resin composition according to claim 5, comprising an acrylonitrile-butadiene-styrene resin.

8. A resin molded article obtained by molding the resin composition according to claim 5.

9. A resin molded article obtained by molding the resin composition according to claim 7.

10. An additive for imparting antimicrobial properties to a resin, comprising the copolymer of any one of claims 1 to 4.

11. The additive of claim 10, wherein the resin is an acrylonitrile-butadiene-styrene resin.

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