JP5277659B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in heat resistance and bleeding resistance and equipped with antistatic ability with less voltage dependence, and to provide a molded article obtained using the same. <P>SOLUTION: The thermoplastic resin composition comprises a thermoplastic resin (A), 0.1-10 pts.wt. of an ambient temperature molten salt (B) which is one or more salts selected from among imidazolium salts, pyridinium salts, ammonium salts, phosphonium salts or sulfonium salts as an antistatic agent, and 1-35 pts.wt. of a thermoplastic polyurethane resin (C) having a glass transition temperature of &le;-30&deg;C, based on 100 pts.wt. of the thermoplastic resin composition. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention is a thermoplastic resin composition comprising a thermoplastic resin, a thermoplastic polyurethane resin, a room temperature molten salt, excellent in heat resistance and bleed resistance, and imparted antistatic ability with little voltage dependence, and using the same It relates to a molded article to be obtained.

  Conventionally, plastic molded products have been used in a wide range of fields due to their excellent workability and mechanical properties. However, because they are electrical insulators, malfunctions of electronic devices due to dust and dirt caused by static electricity, spark discharge, etc. Damage has become a problem. In order to prevent damage due to static electricity, antistatic properties can be imparted to the resin by applying a surfactant or other antistatic agent dissolved in water or solvent to the resin surface, or using an antistatic agent on the resin. A method of kneading is known. The method of applying the antistatic agent to the resin surface is effective in a relatively small amount, but it takes time for the pretreatment of the coating, and there are problems of uneven coating, stickiness, and product contamination. Furthermore, since the bond between the resin and the antistatic agent is a physical bond, the adhesion and friction resistance are inferior, and the conductivity decreases significantly after a long period of time. . On the other hand, the method of kneading the antistatic agent into the resin is relatively easy compared to the method of applying, but it is difficult to produce an effect unless it is used in a large amount, and depending on the type, coloring and deterioration due to heat occur during molding processing. There is something. In addition, since the low molecular weight antistatic agent bleeds out on the surface of the plastic molded product or film after being kneaded, the effect may be lost by wiping cloth or washing with water. Therefore, an antistatic agent free from thermal deterioration and bleed out is strongly desired.

  In general, as a means for preventing static electricity by kneading, conductive fillers and antistatic agents such as carbon materials and metal materials are used, but carbon materials and metal materials color the molded product black and apply voltage Therefore, there is a problem that the conductivity is greatly different. In addition, the polymer antistatic agent has no bleed out and is relatively excellent in heat resistance. However, when used in engineering plastics such as polycarbonate, it is inferior in heat resistance, so it stays at high temperatures such as in an injection molding machine. There is a problem in that it causes thermal deterioration, causing molding defects and functional deterioration. For these reasons, room temperature molten salts with high heat resistance have attracted attention as antistatic agents (Patent Documents 1 and 2).

However, since ordinary temperature molten salts generally have a low molecular weight, there is concern about bleeding on the surface of the molded product. As a method for improving this defect, a polymerized ionic liquid in which a polymerizable group is introduced into a room temperature molten salt and ions are fixed to the polymer main chain or side chain has been proposed (Patent Document 3). However, the polymerization decreases the number of carrier-ions and the mobility of carrier-ions by orders of magnitude, so that excellent conductivity cannot be obtained.
Japanese Patent Laid-Open No. 08-245828 JP 2005-15573 A JP 2006-137585 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a thermoplastic resin composition excellent in heat resistance and bleed resistance and imparting an antistatic ability with little voltage dependence, and a molded product obtained using the same.

  A first invention is a thermoplastic resin composition comprising a thermoplastic resin (A), a room temperature molten salt (B), and a thermoplastic polyurethane resin (C) having a glass transition temperature of −30 ° C. or lower, The thermoplastic resin composition is characterized by being 0.1 to 10 parts by weight of a normal temperature molten salt (B) and 1 to 35 parts by weight of a thermoplastic polyurethane resin (C) with respect to 100 parts by weight of the thermoplastic resin composition.

  The second invention is characterized in that the room temperature molten salt (B) comprises one or more selected from imidazolium-based, pyridinium-based, ammonium, phosphonium-based, or sulfonium-based. It is a thermoplastic resin composition.

  3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic polyurethane resin (C) is composed of a polyester polyol, a diisocyanate, and a chain extender made from adipic acid. It is a thing.

  A fourth invention is a molded article obtained by using the thermoplastic resin composition according to any one of claims 1 to 3.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a thermoplastic resin composition excellent in heat resistance and bleed resistance and imparting antistatic ability with little voltage dependence, and a molded product obtained using the same.

First, the present invention will be described in detail.
The thermoplastic resin composition of the present invention contains a thermoplastic resin (A), a room temperature molten salt (B), and a thermoplastic polyurethane resin (C). The resin composition of the present invention may be a thermoplastic polyurethane resin composition containing a room temperature molten salt at a relatively high concentration, diluted with a thermoplastic resin during molding, or a room temperature molten salt at a final concentration. The adjusted thermoplastic resin composition may be a compound that is used for molding with the same composition without dilution. The thermoplastic resin (A) used in the present invention is not particularly limited as long as a masterbatch can be produced. Polyolefin resins such as polyethylene resin and polypropylene resin, polystyrene resin, ABS resin, AES resin, AS resin, polyvinyl chloride resin, polyester resin, polycarbonate resin, polyamide resin such as nylon 6, nylon 66, nylon 11 and nylon 12, acrylic resin, polylactic acid resin and the like.

  The room temperature molten salt (B) used in the present invention is a generic term for salts that are liquid near room temperature and is also called an ionic liquid, is a liquid in a wide range near room temperature, and has a very low vapor pressure near room temperature. It is a salt composed of a cation and an anion having the characteristics described above, and functions as an antistatic agent. The cation of the room temperature molten salt is imidazolium, pyridinium, ammonium, phosphonium, sulfonium, for example, dialkylimidazolium, trialkylimidazolium, alkylpyridinium, dialkylpyridinium, trialkylpyridinium, 1-fluoroalkylpyridinium, 1- Examples include fluorotrialkylpyridinium, tetraalkylammonium, tetraalkylphosphonium, and trialkylsulfonium.

  More specific examples include 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-propyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-butyl- 3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-octyl-3-methylimidazolium, 1-methyl-3-octylimidazolium, 1-decyl-3-methylimidazolium, 1-dodecyl- 3-methylimidazolium, 1-tetradodecyl-3-methylimidazolium, 1-hexadodecyl-3-methylimidazolium, 1-octadodecyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium 1-propyl-2,3-dimethylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-hexyl-2,3-dimethylimidazolium, 1 -Octyl-2,3-dimethyl Imidazolium 1,2-dimethyl-3-octylimidazolium, 1-butyl-3-ethylimidazolium, 1-hexyl-3-ethylimidazolium, 1-ethyl-3-octylimidazolium, 1-ethyl-3-butyl Imidazolium, 1-ethyl-3-hexylimidazolium, 1-octyl-3-ethylimidazolium, 1,2-diethyl-3,4-dimethylimidazolium, 1-fluoropyridinium, 1-fluoro-2,4, 6-trimethylpyridinium, 1-ethylpyridinium, 1-butylpyridinium, 1-hexylpyridinium, 1-propyl-3-methylpyridinium, 1-butyl-4-methylpyridinium, 1-butyl-3-methylpyridinium, 1-hexyl- 4-methylpyridinium, 1-hexyl-3-methylpyridinium, 1-octyl-4-methylpyridinium, 1-octyl-3-methylpyridinium, 1-butyl-3,4-dimethylpyridinium, 1-butyl 3,5-dimethylpyridinium, trimethylpentylammonium, trimethylhexylammonium, trimethylheptylammonium, trimethyloctylammonium, triethylpropylammonium, triethyl (2-methoxyethyl) ammonium, methyltrioctylammonium, triethylpentylammonium, triethylheptylammonium Dimethylethylpropylammonium, dimethylbutylethylammonium, dimethylethylpentylammonium, dimethylethylhexylammonium, dimethylethylheptylammonium, dimethylethylnonylammonium, dimethylethylheptadecylammonium, dimethyldipropylammonium, dimethylbutylpropylammonium, dimethylpropylpe Tylammonium, dimethylhexylpropylammonium, dimethylheptylpropylammonium, dimethylbutylpentylammonium, dimethylbutylhexylammonium, dimethylbutylheptylammonium, dimethylhexylpentylammonium, diethylheptylmethylammonium, dihexyldimethylammonium, dipropylbutylhexylammonium, dihexyldi Propylammonium, diethylmethylpropylammonium, diethylmethyl (2-methoxyethyl) ammonium, dipropylethylmethylammonium, diethylpropylpentylammonium, diethylmethylpentylammonium, ethylmethylpropylpentylammonium, dipropylmethylpentylammonium, dibutylmethyl Pentyl ammonium jib hexyl methyl ammonium, tri-hexyl tetradecyl phosphonium, triisobutyl methyl phosphonium, tetrabutyl phosphonium, triethyl sulfonium, and the like.

  As an anion of room temperature molten salt, hexafluorophosphate, tetrafluoroborate, methylsulfonic acid, trifluoromethanesulfonic acid, bistrifluoromethanesulfonic acid imide, bispentafluoroethanesulfonic acid imide, biscyanoimide, nitric oxide, acetic acid, Examples thereof include trifluoromethanecarboxylic acid and ethyl sulfate.

  Specific examples of the room temperature molten salt include 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium hydrogen sulfate, 1-butyl-3- Methyl imidazolium methanesulfonic acid, 1-butyl-3-methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium tetrachloroaluminate, 1-butyl-3-methylimidazolium thiocyanate, 1-ethyl-2, 3-dimethylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazole Lithium hydrogen sulfate, 1-ethyl-3-methylimidazolium methanesulfonic acid, 1-ethyl-3-methyl Louis imidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium thiocyanate, 1-methylimidazolium chloride, 1-methylimidazolium hydrogen sulfate, 1,2,3-trimethylimidazolium methyl sulfate, 1-ethyl -3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl -3 methylimidazolium hexafluoroantimonate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-dodecyl-3imidazolium iodide, 1-ethyl-2,3-dimethylimidazolium trifluoromethanesulfonic acid 1-ethyl-3-methylimidazoli Um dicyanamide, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1,2-dimethyl-3-propylimidazolium bis (trifluoro Methylsulfonyl) imide, 1,2-dimethyl-3-propylimidazolium bis (pentafluoroethylsulfonyl) imide, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methyl Imidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium octyl sulfate, 1-butyl-3-methylimidazolium tosylate, 1-ethyl-3 methylimidazolium tosylate, 1-methyl-3-octylimidazo Helium hexafluorophosphate, 1-methyl-3-octylimidazolium tetrafluorobo 4- (3-butyl-1-imidazolio) -1-butanesulfonic acid triflate, 4- (3-butyl-1-imidazolio) -1-butanesulfonate, 1-aryl-3-methylimidazole Rium chloride, 1-benzyl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazolium hexafluorophosphonate, 1-benzyl-3-methylimidazolium tetrafluoroborate, 1-butyl-2,3- Dimethylimidazolium chloride, 1-butyl-3-methylimidazolium 2- (2-methoxyethoxy) -ethyl sulfate, 1-hexyl-3-methylimidazolim hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethane Phonate, 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide, 3-methyl-1-propylpyridinium bis (trifluoro (Romethylsulfonyl) imide, 1-butyl-4-methylpyridinium tetrafluoroborate, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridinium hexafluorophosphate, Tributylmethylammonium methylsulfate, methyl-trioctylammonium bis (trifluoromethylsulfonyl) imide, tetrabutylammonium bis (trifluoromethylsulfonyl) imide, tetraethylammonium trifluoromethanesulfonate, tetrabutylammonium bromide, methyltrioctylammonium thio Salicylate, tetrabutylammonium benzoate, tetrabutylammonium methanesulfonate, tetrabutylammonium nonafluorobuta Sulfonate, tetrabutylammonium heptadecafluorooctane sulfonate, tetrahexylammonium tetrafluoroborate, tetraoctylammonium chloride, tetrapentylammonium thiocyanate, tetrabutylammonium bromide, tetraethylammonium trifluoroacetate, tetrabutylammonium iodide, tetrabutylphosphonium Tetrafluoroborate, trihexyltetradecylphosphonium bis (2,4,4-trimethylpentyl) phosphinate, trihexyltetradecylphosphonium bis (trifluoromethylsulfonyl) amide, trihexyltetradecylphosphonium bromide, trihexyltetradecylphosphonium chloride, Trihexyl tetradecylphosphoni Mudecanoate, trihexyl tetradecylphosphonium dicyanamide, trihexyl tetradecylphosphonium hexafluorophosphate, triisobutylmethylphosphonium tosylate, 3- (triphenylphosphonio) propane-1-sulfonic acid, 3- (triphenylphosphonio) Propane-1-sulfonate, tetrabutylphosphonium p-toluene "sulfonate, triethylsulfonium bis (trifluoromethylsulfonyl) imide.

  As described above, the room temperature molten salt is liquid near room temperature, and its vapor pressure is extremely low, and it has better heat resistance than the surfactants and polymer antistatic agents used as conventional antistatic agents. Yes. In addition, when mixed with a resin, there is no need to dissolve and add in another solvent. Furthermore, since the ions or molecules of the room temperature molten salt are liquid, the interaction between ions or molecules is small, It is presumed that the resin is less likely to agglomerate only at room temperature molten salt, has a relatively good dispersion, and easily exhibits conductivity efficiently.

  The thermoplastic polyurethane resin (B) used in the present invention is composed of a polyol having a terminal active hydrogen having a molecular weight of 500 to 4000, a low molecular weight diol (chain extender) having a molecular weight of 50 to 500, and a diisocyanate, and the chain extender and the diisocyanate. This block copolymer consists of a hard segment made by the reaction of the above and a soft segment made by the reaction of the polyol and diisocyanate. The type of polyol is either an ester system using polyester polyol or an ether system using polyether polyol. May be. By using a thermoplastic polyurethane resin in combination, a thermoplastic polyurethane resin circuit is formed in the thermoplastic resin matrix, a free volume is large at room temperature, and a room temperature molten salt is selectively used in a thermoplastic polyurethane resin having good mobility. It is presumed that the conductivity is obtained more efficiently than the addition of room temperature molten salt to one type of resin. A method for producing the polyester polyol or polyether polyol used in the present invention is not particularly limited, and a known method can be adopted. That is, the polyester polyol is, for example, a direct esterification reaction between an ester-forming derivative such as a low-molecular dicarboxylic acid that gives a desired low-molecular dicarboxylic acid unit or a methyl ester thereof and a low-molecular diol that gives a desired low-molecular diol unit. It is produced by subjecting it to a transesterification reaction and subjecting the resulting low polymer to a polycondensation reaction. Here, as the low-molecular dicarboxylic acid, oxalic acid, succinic acid, glutaric acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, isosebacic acid and other saturated fatty acids, maleic acid or fumaric acid, etc. These unsaturated fatty acids, aromatic acids such as phthalic acid and isophthalic acid, or anhydrides thereof are used alone or in combination. Moreover, the dimer acid obtained by dimerization of an unsaturated fatty acid may be sufficient. Examples of the low molecular weight diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol and the like. Furthermore, triols such as trimethylolpropane, trimethylolethane, hexanetriol, and glycerin, hexaols such as sorbitol, and the like can be used. Polyethers include ring-opening polymerization or copolymerization of cyclic ethers such as ethylene oxide, propylene oxide, trimethylene oxide, butylene oxide, α-methyltrimethylene oxide, 3,3′-dimethyltrimethylene oxide, tetrahydrofuran, dioxane and dioxamine. Polyether glycols or polyoxyalkylene glycols produced by polymerization. The polycarbonate polyol is a method similar to a known method used in the production of a normal polycarbonate such as a polycarbonate from a carbonate compound and bisphenol A, that is, an ester of a carbonate compound and a low molecular diol that gives a desired low molecular diol unit. It can be produced by an exchange reaction. Here, as the carbonate compound, dialkyl carbonates such as diethyl carbonate and dimethyl carbonate, diaryl carbonates such as diphenyl carbonate, alkylene carbonates such as ethylene carbonate, and the like are preferably used. Examples of the diisocyanate used in the present invention include known aliphatic, alicyclic or aromatic diisocyanates. Typically, 4,4′-diphenylmethane diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate, 1, Examples of the diisocyanate include 5-naphthylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and 4,4′-dicyclohexylmethane diisocyanate. As organic diisocyanate, although only 1 type may be used, 2 or more types may be used.

  The glass transition temperature of the thermoplastic polyurethane resin used in the present invention was measured using a solid viscoelasticity measuring device (manufactured by Seiko Denshi Kogyo Co., Ltd.) at a frequency of 1 Hz and a heating rate of 5 ° C./min. The glass transition temperature was the peak position of tan δ.

  The resin composition of the present invention is a thermoplastic polyurethane (C) 1-35 having a normal temperature molten salt (B) of 0.1-10 parts by weight and a glass transition temperature of -30 ° C or less, relative to 100 parts by weight of the thermoplastic resin composition. Contains parts by weight. The addition amount of the room temperature molten salt is preferably 10 parts by weight or less, and the resin composition in this range exhibits bleed resistance due to the intermolecular cohesive force of the urethane group of the thermoplastic polyurethane resin and the height of the segment motion. . Moreover, in the case of 0.1 weight part or more, the outstanding electroconductivity by thermoplastic polyurethane resin combined use is shown. When the amount of the room temperature molten salt is less than 0.1 parts by weight, sufficient antistatic ability is not exhibited due to a decrease in the number of carrier ions. On the other hand, when the amount exceeds 10 parts by weight, the amount of the room temperature molten salt in the resin increases, so that the saturated state occurs and the bleed cannot be sufficiently suppressed. The room temperature molten salt is more preferably 0.3 to 5 parts by weight. The glass transition temperature of the thermoplastic polyurethane resin varies depending on the volume expansion coefficient of the thermoplastic polyurethane resin and the structure of the room temperature molten salt that becomes a steric hindrance factor, and cannot be determined uniformly, but is preferably −30 ° C. or lower. When the temperature is higher than −30 ° C., the free volume at room temperature is small and the segment motion is also small, so that the conductive efficiency is lowered, which is not preferable.

  Production of the thermoplastic resin composition of the present invention is not particularly limited, the thermoplastic resin (A), room temperature molten salt (B), thermoplastic polyurethane resin (C), a general high-speed shear mixer After mixing using a Henschel mixer, super mixer, etc., two-roll, three-roll, pressure kneader, Banbury mixer, single-screw kneading extruder, twin-screw kneading extruder, etc. It is manufactured by extruding into a shape. Further, it is also possible to premix the thermoplastic resin (A) and the thermoplastic polyurethane resin (C) by tumbling and then inject the room temperature molten salt into the extruder using a liquid addition device.

  The thermoplastic resin composition of the present invention thus obtained is, if necessary, a colorant, a nucleating agent, a lubricant, a filler, a stabilizer, a plasticizer, a mold release agent, an ultraviolet absorber, an antioxidant, It is possible to add additives such as flame retardants and antibacterial agents.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The results of evaluation of antistatic ability and bleedability are shown in Table 1.
[Example 1]

Polyester resin ("Easter PETG6763" manufactured by Eastman Chemical Co., Ltd.) 79% by weight as thermoplastic resin (A), room temperature molten salt (B) ("CIL-312" manufactured by Nippon Carlit Co., Ltd.) 1% by weight, thermoplastic polyurethane resin ( C) (Pandex T-1195, glass transition temperature -36 ° C, manufactured by DIC Bayer Polymer Co., Ltd.) 20% by weight, tumbling thermoplastic resin and polyester resin, twin screw extruder (manufactured by Nippon Placon Co., Ltd.) ) To prepare a thermoplastic resin composition. The room temperature molten salt was poured into a twin screw extruder by a liquid addition device.
[Example 2]

(A) Polycarbonate resin ("Iupilon S3000" manufactured by Mitsubishi Engineering Plastics Co., Ltd.) 82% by weight, room temperature molten salt (B) ("CIL-312" manufactured by Nippon Carlit Co., Ltd.), 3% by weight, thermoplastic polyurethane resin (C) A thermoplastic resin composition was prepared in the same manner as in Example 1 using 15% by weight (“T-1195” manufactured by DIC Bayer Polymer Co., Ltd.).
[Example 3]

A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the addition weight ratio of (A) / (B) / (C) was changed to 87/3/10.
[Example 4]

A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the weight ratio of (A) / (B) / (C) was changed to 88/6/6.
[Example 5]

A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the addition weight ratio of (A) / (B) / (C) was changed to 69.8 / 0.2 / 30.
[Example 6]

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the weight ratio of (A) / (B) / (C) was changed to 89/8/3.
[Example 7]

A thermoplastic resin composition was prepared in the same manner as in Example 1 except that (C) was changed to ("T-1180" glass transition temperature -55 ° C, manufactured by DIC Bayer Polymer Co., Ltd.).
[Example 8]

A thermoplastic resin composition was prepared in the same manner as in Example 1 except that (C) was changed to ("T-1185" glass transition temperature -48 ° C, manufactured by DIC Bayer Polymer Co., Ltd.).
[Example 9]

A thermoplastic resin composition was prepared in the same manner as in Example 1 except that (C) was changed to ("T-1190" glass transition temperature -44 ° C, manufactured by DIC Bayer Polymer Co., Ltd.).
[Example 10]

A thermoplastic resin composition was prepared in the same manner as in Example 1 except that (B) was changed to ("1-butyl-3-methylimidazolium tetrachloroaluminate" manufactured by Aldrich).
[Example 11]

A thermoplastic resin composition was prepared in the same manner as in Example 1 except that (B) was changed to ("Tributylmethylammonium methyl sulfate" manufactured by Aldrich).
[Example 12]

A thermoplastic resin composition was prepared in the same manner as in Example 1 except that (B) was changed to ("trihexyltetradecylphosphonium tetrafluoroborate" manufactured by Aldrich).
[Example 13]

  A thermoplastic resin composition was prepared in the same manner as in Example 1 except that (B) was changed to ("Triethylsulfonium bistrifluoromethylsulfonylimide" manufactured by Aldrich).

Comparative example

  [Comparative Example 1]

In Example 1, no thermoplastic polyurethane resin was added, and 99% by weight of a polyester resin (“PETG6763” manufactured by Eastman Chemical Co., Ltd.) as a thermoplastic resin (A), room temperature molten salt (B) (“CIL-312” Japan) A thermoplastic resin composition was prepared using a twin screw extruder (manufactured by Nippon Placon Co., Ltd.) instead of 1% by weight (Carlit). The room temperature molten salt was poured into a twin screw extruder by a liquid addition device.
[Comparative Example 2]

In Example 3, the thermoplastic polyurethane resin was not added, the thermoplastic resin (A) was 97% by weight of a polyester resin (“PETG6763” manufactured by Eastman Chemical Co.), and the ambient temperature molten salt (B) (“CIL-312”) A thermoplastic resin composition was prepared in the same manner as in Comparative Example 1 instead of 3% by weight (manufactured by Nippon Carlit Co., Ltd.).
[Comparative Example 3]

In Example 4, a thermoplastic polyurethane resin was not added, and a polyester resin (“PETG6763” manufactured by Eastman Chemical Co., Ltd.) 97% by weight and a room temperature molten salt (B) (“triethylsulfonium bistrifluoro” were added as the thermoplastic resin (A). A thermoplastic resin composition was prepared in the same manner as in Comparative Example 1 instead of 3% by weight of “methylsulfonylimide” (manufactured by Aldrich).
[Comparative Example 4]

  In Example 2, the thermoplastic polyurethane resin was not added, the polycarbonate resin (“Iupilon S3000”) was 97% by weight as the thermoplastic resin (A), and the normal temperature molten salt (B) (“CIL-312”, Nippon Carlit Co., Ltd.) (Manufactured) A thermoplastic resin composition was prepared in the same manner as in Comparative Example 1 instead of 3% by weight.

  The test pieces obtained in the examples were evaluated according to the following criteria.

[Antistatic evaluation]
(1) The antistatic ability of the molded product was evaluated according to the following criteria.

  Test pieces were prepared from the thermoplastic resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 4 using an injection molding machine. The surface resistance value of a molded plate having a thickness of 3 mm was measured for the obtained test piece using a surface resistance measurement value meter R8340 ULTRA HIGH RESISTANCE manufactured by ADVANTEST. The applied voltage is measured at two points of 500V and 5V.

[Voltage dependency evaluation]
(2) The voltage dependence of the molded product was evaluated according to the following criteria.

  Surfaces of the thermoplastic resin composition test pieces having a thickness of 3 mm obtained in Examples 1 to 13 and Comparative Examples 1 to 4 were measured at an applied voltage of 500 V and 5 V using a surface resistance measurement meter R8340 ULTRA HIGH RESISTANCE manufactured by ADVANTEST. The resistance value was measured. The result here employs the deviation of the resistance value between the two obtained voltages.

○: Deviation of resistance value 2 times less than 10 ^0.5 Δ: Deviation of resistance value 2 times 10 ^0.5 or more and less than 10 ^1.0 ×: Deviation of resistance value 2 times 10 ^1.0 or more
[Bleed evaluation]
(3) The bleeding property of the molded product was evaluated according to the following criteria.

  The molded plate having a thickness of 3 mm was wiped with a cloth dampened with water 10 times, and after wiping with a dry cloth, the low resistance value was measured. Then, it was left to stand for 30 days in an environment of temperature 25 ° C. and humidity 60%, and the resistance value was measured. The result here uses the two deviations in resistance values obtained. The measurement is performed at an applied voltage of 500V.

○: Deviation of resistance value of 2 times less than 10 ^0.3 △: Deviation of resistance value of 2 times 10 ^0.3 or more and less than 10 ^1.0 ×: Deviation of resistance value of 2 times 10 ^1.0 or more

表１から明らかなように、本発明の熱可塑性樹脂組成物は、常温溶融塩の添加量が同一の実施例１と比較例１、実施例２と比較例４、実施例６と比較例２を比較したとき、表面抵抗値が10³~10⁵程度向上し、熱可塑性ポリウレタン樹脂を併用することによる帯電防止能の向上が確認できた。また、本発明の熱可塑性樹脂組成物(実施例１〜１３)は、熱可塑性ポリウレタン樹脂を使用しない熱可塑性樹脂組成物(比較例１〜４)と比較して非電圧依存性、ブリード抑制が確認できた。

As is apparent from Table 1, the thermoplastic resin composition of the present invention has the same amount of room temperature molten salt as Example 1, Comparative Example 1, Example 2, Comparative Example 4, Example 6, and Comparative Example 2. , The surface resistance value was improved by about 10 ³ to 10 ^{5, and} it was confirmed that the antistatic ability was improved by using a thermoplastic polyurethane resin in combination. Further, the thermoplastic resin compositions (Examples 1 to 13) of the present invention are non-voltage dependent and bleed-suppressed compared to the thermoplastic resin compositions not using a thermoplastic polyurethane resin (Comparative Examples 1 to 4). It could be confirmed.

Claims (2)

A thermoplastic resin composition comprising a thermoplastic resin (A) (excluding the thermoplastic polyurethane resin), a room temperature molten salt (B), and a thermoplastic polyurethane resin (C) having a glass transition temperature of −30 ° C. or lower. It is a thing, Comprising: It is 0.1-10 weight part of normal temperature molten salt (B) with respect to 100 weight part of thermoplastic resin compositions, and a thermoplastic polyurethane resin (C) 1-35 weight part ,
The cation of the room temperature molten salt (B) is one or more selected from imidazolium, pyridinium, phosphonium, or sulfonium,
The thermoplastic polyurethane resin (C) comprises a polyester polyol, a diisocyanate, and a chain extender made from adipic acid as a raw material . A molded product obtained by using the thermoplastic resin composition according to claim 1 .