WO2023119645A1

WO2023119645A1 - Polycarbonate resin composition, molded product, and production method for polycarbonate resin composition

Info

Publication number: WO2023119645A1
Application number: PCT/JP2021/048300
Authority: WO
Inventors: 昌志藤田; 雄一松尾
Original assignee: 三菱電機株式会社
Priority date: 2021-12-24
Filing date: 2021-12-24
Publication date: 2023-06-29
Also published as: JPWO2023119645A1

Abstract

A polycarbonate resin composition which comprises: 100 parts by weight of a polycarbonate resin; 0.5-5.0 parts by weight of a phosphonium salt-based ionic liquid; and 0.01-0.09 parts by weight of composite nanofibres.

Description

Polycarbonate resin composition, molded article, and method for producing polycarbonate resin composition

The present disclosure relates to a polycarbonate resin composition, a molded product, and a method for producing a polycarbonate resin composition.

While polycarbonate resin is excellent in transparency, mechanical properties, heat resistance, etc., it has a high surface specific resistivity (10 ¹⁴ Ω/sq or more), so dust such as dust and dirt easily adheres to the surface of the molded product. There is a risk of causing problems such as malfunction when used in electrical equipment parts.

Therefore, an antistatic polycarbonate resin composition to which an ionic liquid with high antistatic performance or a conductive metal oxide is added is being studied. However, if a large amount of an antistatic agent is added in order to improve the antistatic performance, discoloration and a decrease in transparency occur.

As a method of imparting antistatic properties while ensuring transparency, surfactants such as quaternary ammonium salts and sulfonates, conductive polymers such as polythiophene and polyaniline, and conductive metal oxides such as indium oxide and tin oxide are used. is known to be added, and antistatic properties are imparted to polycarbonate resin compositions by adding a single antistatic agent to multiple additions.

For example, in Patent Document 1 (Patent No. 4870256), the antistatic agent is selected from phosphonium sulfonate, potassium and sodium salts of diphenylsulfone-3-sulfonic acid, and potassium and sodium salts of perfluoroalkanesulfonic acid. metal salts are disclosed. Further, Patent Document 2 (Japanese Unexamined Patent Application Publication No. 2009-107286) discloses phosphonium benzenesulfonate and phosphonium naphthylsulfonate as antistatic agents.

Patent No. 4870256 JP 2009-107286 A

However, although the above antistatic agent has a high total light transmittance and ensures transparency, it has a high surface specific resistivity (10 ¹² Ω/sq to 10 ¹³ Ω/sq) and does not have sufficient antistatic properties. I didn't. In addition, since there is a high correlation between antistatic properties and dust adhesion, it is sufficiently effective against both hydrophilic dust stains such as dust and dirt, and hydrophobic dust stains such as soot and oil smoke. was not accepted.

The present disclosure has been made in order to solve the above problems, and provides a polycarbonate resin composition and a molded article that are difficult to adhere to both hydrophilic dust stains and hydrophobic dust stains while ensuring transparency. intended to provide

As a result of intensive studies to solve the above problems, the present inventors have found that the synergistic effect of combining a polycarbonate resin with a phosphonium salt-based ionic liquid and composite nanofibers ensures transparency and hydrophilic dust. It has been found that an antifouling effect is obtained in which both stains and hydrophobic dust stains are difficult to adhere.
The present disclosure relates to the following polycarbonate resin composition.

Containing 100 parts by weight of polycarbonate resin (A), 0.5 to 5.0 parts by weight of phosphonium salt-based ionic liquid (B), and 0.01 to 0.09 parts by weight of composite nanofiber (C), Polycarbonate resin composition.

According to the present disclosure, it is possible to provide a polycarbonate resin composition and a molded article that are resistant to adhesion of both hydrophilic dust stains and hydrophobic dust stains while ensuring transparency.

An embodiment of the present disclosure will be described below.

Embodiment 1.
<Polycarbonate resin composition>
The polycarbonate resin composition of the present embodiment comprises 100 parts by weight of polycarbonate resin (A), 0.5 to 5.0 parts by weight of phosphonium salt-based ionic liquid (B), and 0.01 to 0.01 parts by weight of composite nanofiber (C). 0.09 parts by weight.

In the polycarbonate resin composition of the present embodiment, by containing the polycarbonate resin (A), the phosphonium salt-based ionic liquid (B) and the composite nanofiber (C), transparency is ensured while hydrophilic dust stains are removed. It exhibits an antifouling effect that both hydrophobic dust stains and hydrophobic dust stains are less likely to adhere. The reason for using each of the above components will be described below.

Since there is a high correlation between antistatic properties and dust adhesion properties, it has been common practice to add an antistatic agent to lower the surface specific resistivity in order to improve dust adhesion properties. However, since the polycarbonate resin originally has a high surface resistivity (10 ¹⁴ Ω/sq or more), the addition of an antistatic agent tends not to reduce the surface resistivity. Polycarbonate resins are excellent in transparency, mechanical properties, heat resistance, etc., but when an antistatic agent is added, they tend to cause white turbidity and deterioration of mechanical properties. Therefore, the present inventors considered adding various antistatic agents to the polycarbonate resin in view of the above problems.

First, phosphonium salt-based ionic liquids were investigated as antistatic agents. Addition of a small amount of phosphonium salt-based ionic liquid slightly improved the antistatic properties, but the surface specific resistivity was high (10 ¹² Ω/sq to 10 ¹³ Ω/sq), and sufficient antistatic properties were not obtained. . Moreover, when a large amount of phosphonium salt-based ionic liquid was added to lower the surface specific resistivity, the result was a decrease in transparency.

Next, the present inventors investigated adding composite nanofibers as an auxiliary additive to the phosphonium salt-based ionic liquid. By adding composite nanofibers, the phosphonium salt-based ionic liquid clings to the surface of the nanofibers, and by arranging in the fiber direction, a conductive path is formed, the surface specific resistivity can be lowered, and hydrophilic dust A polycarbonate resin composition to which neither stain nor hydrophobic dust stain adheres easily was obtained.
Each component will be described in detail below.

(Polycarbonate resin (A))
The polycarbonate resin (A) contained in the polycarbonate resin composition of the present disclosure is not particularly limited, and includes various resins. For example, an aromatic polycarbonate produced by a solution method (interfacial polycondensation method) or a melt method (transesterification method) using a dihydric phenol and a carbonate precursor can be used. That is, it is possible to use those produced by reacting them by an interfacial polycondensation method between dihydric phenol and phosgene, a transesterification method between dihydric phenol and diphenyl carbonate, or the like.

Examples of dihydric phenols include various ones, particularly 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxy phenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4′-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)oxide, Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone, etc., or these Examples thereof include halogen-substituted products. In addition, hydroquinone, resorcinol, catechol and the like are also included. These may be used alone or in combination of two or more. Among these, bis(hydroxyphenyl)alkanes are preferred, and bisphenol A is more preferred.

Carbonate precursors include carbonyl halides, carbonyl esters, haloformates and the like, specifically phosgene, dihaloformates of dihydric phenols, diphenyl carbonate, dimethyl carbonate, diethyl carbonate and the like.

Polycarbonate resin (A) includes not only new materials but also polycarbonate resins recycled from used products. Any commercially available grade may be used, but an optical grade with high transmittance is desirable. For example, Iupilon ML200, ML300, ML400, HL3003, HL3503 (Mitsubishi Engineering-Plastics Co., Ltd.), SD Polyca 303-10, 303-30 (Sumika Polycarbonate Co., Ltd.), Lexan LS-1, LS-2, LS -3 (SABIC Innovative Plastics Japan LLC), Panlite L-1225Z, L-1225ZL (Teijin Ltd.), Toughlon LC1500, LC1700 (Idemitsu Kosan Co., Ltd.) and the like can be used.

(Phosphonium salt-based ionic liquid (B))
The polycarbonate resin composition of the present disclosure contains a phosphonium salt-based ionic liquid (B). By containing the phosphonium salt-based ionic liquid (B), the antistatic property (dust adhesion prevention property) can be improved.

Phosphonium salt-based ionic liquids (B) include tributyldodecylphosphonium bis(trifluoromethanesulfonyl)imide, tributyldodecylphosphonium bromide, tetrabutylphosphonium dodecylbenzenesulfonate, trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide, triethyl pentylphosphonium bis(trifluoromethylsulfonyl)imide, triethyloctylphosphonium bis(trifluoromethylsulfonyl)imide, tri-n-butylmethylphosphonium bis(trifluoromethylsulfonyl)imide, tetrabutylphosphonium tetraphenylborate and the like. . From the viewpoint of availability, tributyldodecylphosphonium bis(trifluoromethanesulfonyl)imide, tributyldodecylphosphonium bromide, and tetrabutylphosphonium dodecylbenzenesulfonate are preferably used.

Examples of tributyldodecylphosphonium bis(trifluoromethanesulfonyl)imide include, for example, tributyldodecylphosphonium bis(trifluoromethanesulfonyl)imide (Fujifilm Wako Pure Chemical Industries, Ltd.), IL-AP3 (Koei Chemical Industry Co., Ltd.), and the like. Tributyldodecylphosphonium bromide (Fujifilm Wako Pure Chemical Industries, Ltd.) can be used as tributyldodecylphosphonium bromide, and Elekat S-418 (Takemoto Oil & Fat Co., Ltd.) can be used as tetrabutylphosphonium dodecylbenzenesulfonate.

The content of the phosphonium salt-based ionic liquid (B) in the present disclosure is 0.5 to 5.0 parts by weight, preferably 0.5 to 4.0 parts by weight, relative to 100 parts by weight of the polycarbonate resin. , more preferably 0.5 to 3.0 parts by weight. When the content of the phosphonium salt-based ionic liquid (B) exceeds 5.0 parts by weight, the thermal stability at high temperatures is significantly reduced, which not only tends to cause coloration, but also greatly reduces the mechanical properties. be. When the content of the phosphonium salt-based ionic liquid (B) is less than 0.5 parts by weight, the dust adhesion prevention property is deteriorated.

(Composite nanofiber (C))
The polycarbonate resin composition of the present disclosure contains composite nanofibers (C). By containing the composite nanofiber (C), the antistatic property (dust adhesion prevention property) can be improved.

A composite nanofiber (C) in the present disclosure refers to a fiber having a nanometer-order diameter formed by combining two or more metal oxides. Examples of metal oxides include silicon oxide (silica), aluminum oxide (alumina), zinc oxide, titanium oxide, calcium oxide, tin oxide, and indium oxide, with alumina and silica being preferred. As the composite nanofiber (C), a nanofiber obtained by combining alumina and silica is preferable.

The composite nanofiber (C) preferably has an average fiber diameter of 100 nm or less. This is because when the average fiber diameter of the composite nanofibers (C) exceeds 100 nm, Rayleigh scattering occurs and the transparency decreases. From the viewpoint of transparency, the average fiber diameter of the composite nanofibers (C) is more preferably 60 nm or less, and even more preferably 30 nm or less. Although the shape of the composite nanofiber (C) is not particularly limited, it may be fibrous, rod-like, cylindrical, hollow rod-like, core-shell fibrous, etc. Core-shell fibrous is preferred.

The average fiber diameter of the composite nanofibers (C) is determined by taking electron microscope images of a sufficient number (for example, 100 or more) of the composite nanofibers (C) using an electron microscope (SEM, TEM, etc.). It is obtained by measuring the diameter (diameter) of the composite nanofiber (C) and averaging it arithmetically.

In addition, the composite nanofiber (C) has a refractive index at a sodium D line wavelength of 589.3 nm that is close to the refractive index value of the polycarbonate resin (A) at a sodium D line wavelength of 589.3 nm, which is 1.58. Preferably. When the refractive index value of the composite nanofiber (C) is farther than 1.58, the difference between the refractive index of the polycarbonate resin (A) and the composite nanofiber (C) causes scattering or This is because a phenomenon such as refraction occurs and the transparency is lowered. From the viewpoint of transparency, the refractive index value of the composite nanofiber (C) is preferably in the range of 1.40 to 2.00, more preferably in the range of 1.50 to 1.80, and more preferably 1.50 to 1.50. A range of 0.70 is more preferred, and a range of 1.58 to 1.60 is even more preferred.

To adjust the refractive index, it can be achieved with a compound that combines metal oxides with different refractive indexes.

As the composite nanofiber (C), for example, R30SP-M2, R30SP-H1 (Admatechs Co., Ltd.), etc. can be used.

The content of the composite nanofiber (C) in the present disclosure is 0.01 to 0.09 parts by weight, preferably 0.02 to 0.08 parts by weight, with respect to 100 parts by weight of the polycarbonate resin. It is preferably 0.02 to 0.07 parts by weight. If the content of the composite nanofibers (C) exceeds 0.09 parts by weight, the haze may increase and transparency may not be obtained. If the content of the composite nanofibers (C) is less than 0.01 parts by weight, the dust adhesion prevention property is deteriorated.

(Additive)
The polycarbonate resin composition of the present disclosure may contain additives such as heat stabilizers, ultraviolet absorbers, and light stabilizers as long as they do not impede the purpose of the present disclosure.

[Heat resistant stabilizer]
By containing the ionic liquid (B) and the composite nanofiber (C), the polycarbonate resin composition of the present disclosure causes hydrolysis, lowers the thermal stability, and yellows, so the thermal stability is improved. A heat stabilizer may be included in order to

As the heat-resistant stabilizer, it is preferable to use antioxidants such as hindered phenol-based, phosphorus-based, and sulfur-based antioxidants, which may be used alone or in combination of two or more.

The amount of the heat stabilizer added in the present disclosure is not particularly limited, and the composition ratio when two or more types are mixed is not particularly limited, but it can be adjusted on a case-by-case basis depending on the required physical properties. desirable.

Examples of hindered phenol antioxidants include 2,6-di-tert-butyl-p-cresol, tetrakis[methylene-3-(3′,5′-di-tert-butyl-4′-hydroxy phenyl)propionate]methane, stearyl β-(3′,5′-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis[1,1-dimethyl-2-[β-(3-tert -butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, 1,3,5-trimethyl-2,4,6- known tris(3',5'-di-tert-butyl-4-hydroxybenzyl)benzene, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] things are mentioned. Among these, tetrakis[methylene-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate]methane, stearyl β-(3′,5′) are preferred from the viewpoint of heat stability. -di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy] Ethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane is preferred.

Phosphorus-based antioxidants include, for example, tris(2,4-di-tert-butylphenyl)phosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylmonodecylphosphite, pentaerythritol bis(2,6 -di-tert-butyl-4-phenylphosphite), 2,2′-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite, distearylpentaerythritol diphosphite, tri(mono nonylphenyl)phosphite, alkanol (C=12-16) 4,4′-isopropylidenediphenol triphenylphosphite polycondensate, bis[2,4-di-tert-butyl-6-methylphenyl]ethylphosphite phyto, pentaerythritol bis(2,4-di-tert-butylphenyl phosphite), triallyl phosphite, tetrakis(2,4-tert-butylphenyl)-4,4'-biphenyldiphosphonate, etc. are listed. Among these, from the viewpoint of heat resistance stability, tris(2,4-di-tert-butylphenyl)phosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylmonodecylphosphite, pentaerythritol bis(2, 6-di-tert-butyl-4-phenylphosphite), 2,2′-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite are preferred.

Examples of sulfur-based antioxidants include pentaerythritol tetrakis(3-laurylthiopropionate), dilauryl-3,3'-thiodipropionate, dioctadecyl-3,3'-thiodipropionate, and the like. A publicly known thing is mentioned. Among these, pentaerythritol tetrakis(3-laurylthiopropionate) is preferred from the viewpoint of heat resistance stability.

The content of the heat resistant stabilizer in the present disclosure is preferably 0.05 to 10 parts by weight, more preferably 0.05 to 3.0 parts by weight, with respect to 100 parts by weight of the polycarbonate resin (A).

[Ultraviolet absorber]
The polycarbonate resin composition of the present embodiment is often used for outdoor products and yellows due to ultraviolet rays, so it may contain an ultraviolet absorber.

UV absorbers include, for example, hydroxybis(dimethylbenzyl)phenylbenzotriazole, 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole, 2,2′-methylenebis[6-(2H-benzo triazol-2-yl)-4-tert-octylphenol], 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methyl phenyl)-5-chlorobenzotriazole, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol), 2 , 4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine).

Among the above, from the viewpoint of weather resistance stability, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)- 4-tert-octylphenol], 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol), 2,4 ,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine) is preferred. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

The amount of the ultraviolet absorber added in the present disclosure is not particularly limited, and the composition ratio when two or more types are mixed is not particularly limited, but it can be adjusted on a case-by-case basis depending on the required physical properties. desirable.

The content of the ultraviolet absorber in the present disclosure is preferably 0.05 to 10 parts by weight, more preferably 0.05 to 3.0 parts by weight, relative to 100 parts by weight of the polycarbonate resin (A).

[Light stabilizer]
The polycarbonate resin composition of the present disclosure is often used for outdoor products and may contain a light stabilizer because it yellows when exposed to ultraviolet rays.

Light stabilizers include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, tetrakis(2,2,6,6-tetramethyl -4-piperidyl)butane-1,2,3,4-tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid, and 1,2,3,6,6-pentamethyl-4-piperidinol, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane mixed ester, bis(2,2,6,6 -tetramethyl-4-piperidyl) sebacate and other known compounds.

Among the above, from the viewpoint of weather resistance stability, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,6,6-pentamethyl-4-piperidinol, and 3,9-bis(2- Mixed esters with hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane are preferred. The above light stabilizers may be used alone or in mixtures of two or more.

The amount of the light stabilizer added in the present disclosure is not particularly limited, and the composition ratio when two or more types are mixed is not particularly limited, but it can be adjusted on a case-by-case basis depending on the required physical properties. desirable.

The content of the light stabilizer in the present disclosure is preferably 0.05 to 10 parts by weight, more preferably 0.05 to 3.0 parts by weight, relative to 100 parts by weight of the polycarbonate resin (A).

(Other additives)
Other additives that can be used in the present disclosure include antistatic agents, plasticizers, release agents, flame retardants, flame retardant aids, dyes, pigments, etc., as long as they do not interfere with the purpose of the present disclosure. .

Antistatic agents include trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide, triethylpentylphosphonium bis(trifluoromethylsulfonyl)imide, triethyloctylphosphonium bis(trifluoromethylsulfonyl)imide, tri-n-butylmethyl Phosphonium bis(trifluoromethylsulfonyl)imide, phosphonium salt-based ionic liquid (B) such as tetrabutylphosphonium tetraphenylborate, tributylmethylammonium bis(trifluoromethylsulfonyl)imide (FC-4400, 3M Japan Ltd.) ammonium salt-based ionic liquids such as N-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide (CIL-312, Nihon Carlit Co., Ltd.) pyridinium salt-based ionic liquids, imidazolium salt-based ionic liquids, Any known ionic liquid such as pyrrolidinium salt-based ionic liquid can be used.

The plasticizer can be arbitrarily selected from known ones such as polyethylene glycol, polyamide oligomer, ethylene bis-stearamide, phthalate ester, adipate ester, polystyrene oligomer, polyethylene wax, silicone oil and mineral oil. can.

The mold release agent is arbitrarily selected from known substances such as polyethylene wax, silicone oil, stearyl phosphite, long-chain carboxylic acid, long-chain carboxylic acid metal salt, higher fatty acid ester of monohydric or polyhydric alcohol, and the like. be able to.

Flame retardants include phosphorus-based flame retardants such as bisphenol A bis (diphenyl phosphite), tricresyl phosphate, triphenyl phosphate, tris-3-chloropropyl phosphate, 2,2-bis[4-(3,3- Brominated flame retardants such as dibromopropoxyl)-3,5-dibromophenyl]propane, bis(3,5-dibromo-4-dibromopropyloxyphenyl)sulfone, ethylenebispentabromobenzene, hexabromocyclododecane, silicones It can be used by arbitrarily selecting from publicly known flame retardants, hydroxide-based flame retardants such as magnesium hydroxide and aluminum hydroxide.

The flame retardant aid can be arbitrarily selected from antimony compounds such as antimony trioxide and others.

<Method for producing polycarbonate resin composition>
The method for producing the polycarbonate resin composition of the present disclosure is not particularly limited, and a wide range of known methods for producing a polycarbonate resin composition can be employed. The fibers (C) and optional additives are mixed and kneaded. As the kneading method, for example, a method using any physical blend such as melt kneading, solvent cast blend, latex blend, polymer complex, etc. can be used, but the melt kneading method is preferred. The melt-kneading temperature is not particularly limited, but is usually in the range of 240 to 320°C.

Examples of equipment used for the kneading include a tumbler, a Henschel mixer, a rotary mixer, a super mixer, a ribbon tumbler, and a V blender. and pelletize. A single-screw or multi-screw extruder is generally used for melt-kneading pelletization, but a Banbury mixer, a roller, a co-kneader, a blast mill, a Prabender Brautograph, or the like can also be used, and these can be used batchwise or continuously. drive wisely.

In addition, resin pellets, hydrolysis resistance improvers, and other additives are mixed without melt-kneading, and the mixed components are used as a molding resin, and melt-kneaded in a heating cylinder of a molding machine, so-called mold blending. It is also possible to implement in

Embodiment 2.
A molded article according to the present embodiment is made of the polycarbonate resin composition described above. In the molded article according to the present embodiment, since it is made of the above-described polycarbonate resin composition, it is possible to obtain an effect that both hydrophilic dust stains and hydrophobic dust stains are difficult to adhere while ensuring transparency. be.

The molded article of the present embodiment is obtained by melt-kneading the polycarbonate resin composition containing the polycarbonate resin (A), the phosphonium salt-based ionic liquid (B), and the composite nanofiber (C), pelletizing it, and performing various moldings. It can be manufactured by molding by a method. It is also possible to directly mold the resin melted and kneaded by an extruder without going through pellets.

The shape of the molded product is not particularly limited, but can be appropriately selected according to the application and purpose of the molded product. For example, plate-like, plate-like, rod-like, sheet-like, film-like, cylindrical, annular, circular, elliptical, porous, foam, polygonal, odd-shaped, hollow, frame-like, box-like, etc. A panel shape and the like can be mentioned. Specifically, there are various shapes such as automotive interior panels, automotive (motorcycle) headlamp lenses, windows, housings, and special shapes. In addition, the surface of the molded product may have an uneven shape transferred thereto, or may have a three-dimensional shape having a three-dimensional curved surface. Furthermore, when used in the form of a sheet, film, plate, or the like, it may be a multilayer structure laminated with other resin sheets.

In addition, the molding method is not particularly limited, and conventionally known molding methods can be employed, including an injection molding method, an injection compression molding method, an extrusion molding method, a profile extrusion method, a transfer molding method, a blow molding method, and a gas-assisted blow molding. method, blow molding method, extrusion blow molding, IMC (in-mold coating) molding method, rotational molding method, multi-layer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method, pressure molding method , inflation molding, and the like. Furthermore, surface treatments such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc., which are usually used industrially, can also be applied.

(Total light transmittance)
The molded article of the present embodiment has excellent transparency even at a thickness of about 0.5 to 6.0 mm. % or more.

Here, the total light transmittance refers to all transmitted light when the light equivalent to the D65 light source is incident on the measurement object, and the D65 light source refers to the light that reproduces the outdoor lighting environment. say. Taking the state without a test piece as 100%, the closer the numerical value is to 100%, the more transparent it is.

The total light transmittance is measured, for example, according to JIS K7361-1:1997 "Plastics-Testing method for total light transmittance of transparent materials-Part 1: Single beam method", using a thickness of 2.0 mm. Measurement can be performed at a temperature of 23° C. using a molded product with an ultraviolet-visible-near-infrared (UV-Vis-NIR) spectrophotometer (Solid Spec-3700 DUV manufactured by Shimadzu Corp.).

(haze)
In the molded article of the present embodiment, the haze of the molded article having a thickness of 2.0 mm is 7% or less, preferably 6% or less.

Here, haze refers to the degree of light scattering, even in materials that do not absorb light, as light may scatter inside the material and become opaque. A lower value means more transparency.

Haze, for example, using a molded product with a thickness of 2.0 mm, using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd. NDH2000 ) can be measured at a temperature of 23° C. with a D65 light source.

Moreover, haze can be calculated by the following formula (1).
Haze (%)=diffused light component/total light transmittance×100 Equation (1)
Light included in the total light transmittance includes a parallel light component and a diffused light component, and the haze quantifies the proportion of the diffused light component in the total light transmittance.

The present disclosure will be described in detail below with examples, but the present disclosure is not limited to these.

<Evaluation method>
Evaluation was performed by the following method. The test piece used for the following evaluation is a flat plate test piece (length 100 mm x width 100 mm x thickness 2.0 mm), which was evaluated after being left for one week in an environment of temperature 23°C and humidity 50%. .

(1) Transparency (total light transmittance)
JIS K7361-1: 1997 "Plastics - Test method for total light transmittance of transparent materials - Part 1: Single beam method" Using the above flat test piece, ultraviolet visible near infrared (UV -Vis-NIR) was measured at a temperature of 23°C with a spectrophotometer (Solid Spec-3700 DUV manufactured by Shimadzu Corporation). A total light transmittance of 86% or more was considered good.

(2) Transparency (Haze)
JIS K7136: 2000 "Plastics - Determining the haze of transparent materials" is measured using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.) using the above flat plate test piece, with a D65 light source at a temperature of 23 ° C. measured in A haze of 7% or less was considered good.

(3) Antistatic properties (surface specific resistivity)
Using the flat plate test piece, the resistivity was measured under the following test conditions with a resistivity meter (Hiresta UP MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd.). A smaller value indicates better antistatic properties. A case where the surface specific resistivity was less than 10 ¹² Ω/sq was rated as "A", and a case where the surface specific resistivity was 10 ¹² Ω/sq or more was rated as "B".
[Test condition]
Voltage: 1000V
Time: 60 seconds Temperature: 23°C
Humidity: 50%

(4) Adhesiveness to Dust A powder conforming to JIS Z8901:2006 "test powder and test particles" was used. Kanto loam (11 types of JIS test powder 1) is used for hydrophilic dust adhesion evaluation, and carbon black (12 types of JIS test powder 1) is used for hydrophobic dust adhesion evaluation. bottom.
For evaluation of dust adhesion, after blowing a certain amount (5 g) of dust onto the surface of the molded product with air, the surface of the molded product was observed at 100x with a digital microscope (manufactured by Keyence Corporation, VHX-5000). The dust adhesion rate (dust adhesion area ratio) was determined by image processing. A case where the dust adhesion rate is less than 4% is indicated as "A", and a case where the dust adhesion rate is 4% or more is indicated as "B".

(5) Comprehensive judgment When total light transmittance is 86% or more, haze is 7% or less, surface resistivity is less than 10 ¹² Ω / sq, and hydrophilic and hydrophobic dust adhesion rate is less than 4% "A" was indicated, and "B" was indicated when even one of the above items was not satisfied.

<Examples 1 to 10, Comparative Examples 1 to 11>
Each component in the composition ratio shown in Tables 1 and 2 is mixed and melt-kneaded at 280 ° C. using a twin-screw kneading extruder (TEX-26SX manufactured by Shibaura Industry Co., Ltd.) to obtain a polycarbonate of 3 to 5 mm. A pellet of the resin composition was produced.

The obtained pellets were made into flat test pieces for evaluation (length 100 mm x width 100 mm x thickness 2 mm) (Examples 1 to 10, Molded as Comparative Examples 1-11). The basic conditions for injection molding were a resin temperature of 280°C and a mold temperature of 80°C.

Each component shown in Tables 1 and 2 (each component in symbol notation) is as follows.

[Polycarbonate resin: A component]
A-1: Iupilon HL3503 manufactured by Mitsubishi Engineering-Plastics Co., Ltd.
A-2: Toughlon LC1500 manufactured by Idemitsu Kosan Co., Ltd.
A-3: SD polycarbonate 303-30 manufactured by Sumika Polycarbonate Co., Ltd.
A-4: Panlight L-1225ZL manufactured by Teijin Limited
A-5: Iupilon HL3003 manufactured by Mitsubishi Engineering-Plastics Co., Ltd.
A-6: Iupilon SGH1010A manufactured by Mitsubishi Engineering-Plastics Co., Ltd. (10 parts by weight of glass fiber)

[Phosphonium salt-based ionic liquid: B component]
(B-1)
Tributyldodecylphosphonium bis(trifluoromethanesulfonyl)imide [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
(B-2)
Tetrabutylphosphonium dodecylbenzenesulfonate [Elecut S-418 manufactured by Takemoto Yushi Co., Ltd.]
(B-3)
Tributyldodecylphosphonium bromide [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
(B-4)
Tributyldodecylphosphonium bis(trifluoromethanesulfonyl)imide [IL-AP3 manufactured by Koei Chemical Industry Co., Ltd.]

[Ammonium salt-based ionic liquid, pyridinium salt-based ionic liquid: Component B']
(B'-1)
Tributylmethylammonium bis(trifluoromethylsulfonyl)imide [FC-4400 manufactured by 3M Japan Co., Ltd.]
(B'-2)
N-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide [CIL-312 manufactured by Nippon Carlit Co., Ltd.]

[Composite nanofiber: C component]
(C-1)
Nanofibers composed of a composite of alumina and silica [R30SP-H1 manufactured by Admatechs Co., Ltd.] (average fiber diameter: 2 to 50 nm, refractive index: 1.60)
(C-2)
Nanofibers composed of a composite of alumina and silica [R30SP-M2 manufactured by Admatechs Co., Ltd.] (average fiber diameter: 2 to 50 nm, refractive index: 1.58)

[Metal oxide: C' component]
(C'-1)
Antimony-doped tin oxide (ATO) [FS-10P manufactured by Ishihara Sangyo Co., Ltd.] (average fiber diameter: 10 to 20 nm, refractive index: 2.0 to 2.2)

Tables 1 and 2 show the evaluation results of (1) to (4) above and (5) overall judgment for the obtained flat test pieces for evaluation (Examples 1 to 10 and Comparative Examples 1 to 11).

From the evaluation results shown in Table 1, the molded articles made of the polycarbonate resin composition that satisfies the constituent requirements of the present disclosure are excellent in transparency and exhibit both hydrophilic dust stains and hydrophobic dust stains. It can be confirmed that a polycarbonate resin composition exhibiting an antifouling effect that is difficult to adhere to is obtained.

On the other hand, Comparative Example 1 was inferior in antistatic property and dust adhesion property because it did not contain B component and C component. Comparative Example 2 contained the B component but did not contain the C component, so that the transparency and hydrophilic dust adhesion properties were improved, but the antistatic and hydrophobic dust adhesion properties were inferior. Comparative Example 5 contained the C component but did not contain the B component, and thus was inferior in antistatic property and dust adhesion property as in Comparative Example 1. From these results, it can be confirmed that inclusion of all components A to C is a necessary constituent element in the present disclosure.

In addition, although Comparative Examples 7 to 10 contain all of the A to C components, the content of the C component in Comparative Example 7 and the content of the B component in Comparative Example 9 are higher than the specified amounts, respectively. and dust adhesion were improved, but the transparency was poor. In addition, since the content of component C in Comparative Example 8 and the content of component B in Comparative Example 10 were each less than the specified amount, the transparency was improved, but the antistatic property and dust adhesion property were inferior. rice field. From these results, it can be confirmed that the inclusion of all components A to C and the inclusion of each specified amount is a necessary constituent requirement in the present disclosure.

Further, Comparative Example 3 contained an ammonium salt-based ionic liquid (B'-1) instead of the B component, and Comparative Example 4 contained a pyridinium salt-based ionic liquid (B'-2) instead of the B component. Therefore, it was inferior in antistatic properties and hydrophobic dust adhesion properties. From these results, it can be confirmed that the phosphonium salt-based ionic liquid (component B) is the most suitable ionic liquid.

In addition, Comparative Example 6 contained antimony-doped tin oxide (C'-1) instead of the C component, so it was inferior in transparency, antistatic property, and hydrophobic dust adhesion rate. Further, Comparative Example 11 contained glass fiber (A-6) instead of the C component, and therefore was inferior in antistatic property and dust adhesion rate. From these results, it can be confirmed that composite nanofibers are optimal as the C component.

Although not shown in Tables 1 and 2, evaluation of mechanical properties (tensile strength, tensile elongation at break and Charpy impact strength) was performed in Example 1 and Comparative Example 1, and equivalent evaluation results were obtained. It can be confirmed that even if components B to C are blended with component A, no deterioration in mechanical properties is observed.

The embodiments and examples disclosed this time should be considered illustrative in all respects and not restrictive. The scope of the present disclosure is indicated by the scope of claims rather than the above description, and is intended to include all changes within the meaning and scope of equivalence to the scope of claims.

Claims

A polycarbonate resin composition containing 100 parts by weight of a polycarbonate resin, 0.5 to 5.0 parts by weight of a phosphonium salt-based ionic liquid, and 0.01 to 0.09 parts by weight of composite nanofibers.
The phosphonium salt-based ionic liquid according to claim 1, comprising at least one selected from the group consisting of tributyldodecylphosphonium bis(trifluoromethanesulfonyl)imide, tributyldodecylphosphonium bromide and tetrabutylphosphonium dodecylbenzenesulfonate. Polycarbonate resin composition.
The polycarbonate resin composition according to claim 1 or 2, wherein the composite nanofibers are a composite of alumina and silica.
A molded article made of the polycarbonate resin composition according to any one of claims 1 to 3.
A method for producing the polycarbonate resin composition according to any one of claims 1 to 3,
A method for producing a polycarbonate resin composition obtained by melt-kneading a polycarbonate resin, a phosphonium salt-based ionic liquid, and composite nanofibers.