JP2011184647A - Antistatic agent for polycarbonate resin and polycarbonate resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic agent for a polycarbonate resin in which the transparency of a resin is not lowered and the resin is not colored even if the agent is added to the polycarbonate resin, and which has heat resistance which can bear a processing temperature of the polycarbonate resin, and is excellent in durability of an antistatic effect, and to provide a polycarbonate resin composition to which the antistatic agent is added. <P>SOLUTION: The antistatic agent for a polycarbonate resin comprises a compound expressed by General formula (1): R<SP>1</SP>C(O)XCH<SB>2</SB>CH<SB>2</SB>SO<SB>3</SB><SP>-</SP>M. In formula (1), R<SP>1</SP>denotes a 1-30C alkyl group, X denotes an oxygen atom or -N(CH<SB>3</SB>)- group, and M denotes an alkali metal ion, an ammonium ion or a phosphonium ion expressed by General formula (2): P<SP>+</SP>(R<SP>2</SP>)(R<SP>3</SP>)(R<SP>4</SP>)(R<SP>5</SP>), in formula (2), R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>and R<SP>5</SP>each independently denote a 1-18C alkyl group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antistatic agent for a polycarbonate resin and a polycarbonate resin composition, and in particular, an antistatic agent for a polycarbonate resin that has good heat resistance and does not impair the transparency of the resin even when added to the polycarbonate resin. The present invention relates to a polycarbonate resin composition containing an antistatic agent.

Polycarbonate resins are excellent in heat resistance, moldability, mechanical properties, etc., and are widely used as electrical and electronic members, medical members, optical members, and other various molded products.
Polycarbonate, like other plastics, is characterized by high electrical insulation, but on the contrary, it is hard to dissipate static electricity, so that dust adheres to the product, electric shocks to workers, device meanings, and IC chip malfunctions. There is a problem that occurs.
Therefore, hitherto, various antistatic agents for plastics including polycarbonate have been studied.

Antistatic agents include kneading types and coating types, but the coating type is not only inferior in sustainability, but a large amount of organic substances are applied to the surface of the product. There was a problem of being contaminated.
Therefore, a kneading type antistatic agent having no such problems has been mainly studied (Patent Documents 1 to 3).

However, since polycarbonate resins are often used in resin products that make use of high transparency, conventional kneading-type antistatic agents, when added to polycarbonate resins, lower the transparency of the resin and increase the value of the resin product. There was a problem of lowering.
Further, since the polycarbonate resin has a high melting point and is heat-molded at a high temperature, there are problems that the antistatic agent is decomposed by heat and that the resin is colored due to the antistatic agent.

Conventionally, alkyl sulfonates, alkyl benzene sulfonates, and the like have been used as kneading-type antistatic agents used in synthetic resins. Among them, a system using an alkyl (aryl) sulfonate has been well studied. Examples of a large antistatic effect include those in which the secondary position of an alkane is substituted with a sulfonic acid metal salt (Patent Document 4), a phosphonium salt. (Patent Document 5) is disclosed.
However, although these sulfonate-based antistatic agents have a high antistatic effect, their durability and heat resistance are not sufficient, and the coloring resistance of the resin to which the antistatic agent is added is not sufficient. was there.

JP 7-292234 A JP 2002-60734 A JP-A-9-176497 JP-A-5-222241 JP-A-62-230835

As a result of intensive studies to solve the above problems, the present inventors have found that an alkali metal salt, an ammonium salt or a specific phosphonium salt of an ester compound of fatty acid and isethionic acid or an amide compound of fatty acid and N-methyltaurine The heat resistance is good, and adding this to the polycarbonate resin not only does not color the resin, but also does not reduce the transparency of the resin, and a polycarbonate resin having excellent antistatic performance can be obtained. As a result, the present invention has been completed.
Therefore, the first object of the present invention is to add heat resistance to the polycarbonate resin without lowering the transparency of the resin, coloring the resin, and withstanding the processing temperature of the polycarbonate resin. An object of the present invention is to provide an antistatic agent for polycarbonate resin which is excellent in sustainability of an antistatic effect.
The second object of the present invention is to provide a polycarbonate resin composition capable of obtaining a molded article excellent in durability of the antistatic effect, transparency and coloration resistance.

但し、式（１）中のＲ^１は炭素原子数１〜３０のアルキル基、Ｘは酸素原子又は−Ｎ(ＣＨ_３)−基であり、Ｍは、アルカリ金属イオン、アンモニウムイオン、又は下記一般式（２）で表されるホスホニウムイオンである。

但し、式（２）中のＲ^２、Ｒ^３、Ｒ^４及びＲ^５は各々独立に、炭素原子数１〜１８のアルキル基である。 That is, the antistatic agent for polycarbonate resin is 0.01 to 100 parts by mass of the antistatic agent for polycarbonate resin, and 100 parts by mass of the polycarbonate resin, characterized by comprising a compound represented by the following general formula (1). It is a polycarbonate resin composition characterized by containing 20 mass parts.

However, ^{R 1} in the formula (1) is an alkyl group having 1 to 30 carbon atoms, X is an oxygen atom or -N (CH ₃₎ - is a group, M is an alkali metal ion, an ammonium ion, or the following general It is a phosphonium ion represented by Formula (2).

However, each independently ^{R 2,} R 3, ^{R 4} and ^{R 5} in formula (2) is an alkyl group having 1 to 18 carbon atoms.

  The antistatic agent of the present invention is not only excellent in heat resistance and sustainability of the antistatic effect, but also by adding to the polycarbonate resin, the antistatic effect and transparency of the resin are not lowered, and the color resistance is also reduced. An excellent polycarbonate resin can be provided.

但し、式（１）中のＲ^１は炭素原子数１〜３０のアルキル基、Ｘは酸素原子又は−Ｎ(ＣＨ_３)−基であり、Ｍは、アルカリ金属イオン、アンモニウムイオン又は下記一般式（２）で表されるホスホニウムイオンである。

但し、式（２）中のＲ^２、Ｒ^３、Ｒ^４及びＲ^５は、各々独立に、炭素原子数１〜１８のアルキル基である。 The present invention is described in detail below.
The antistatic agent of this invention consists of a compound represented by General formula (1).

However, ^{R 1} is an alkyl group having 1 to 30 carbon atoms in the formula (1), X is an oxygen atom or -N (CH ₃₎ - is a group, M is an alkali metal ion, an ammonium ion or the following general formula It is a phosphonium ion represented by (2).

However, ^{R 2,} R 3, ^{R 4} and ^{R 5} in formula (2) are each independently an alkyl group having 1 to 18 carbon atoms.

Specific examples of R ¹ in the general formula (1) include methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, isobutyl, amyl, isoamyl, tertiary amyl, pentyl, hexyl, Heptyl, 2-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl And linear or branched alkyl groups such as nonadecyl, eicosyl, behenyl and tricosyl.
The number of carbon atoms of R ¹ is preferably 3 to 21, more preferably 5 to 17, and most preferably 8 to 15 from the viewpoints of antistatic properties, transparency, and color resistance. .

  M in the general formula (1) is an alkali metal ion, an ammonium ion or a phosphonium ion represented by the general formula (2). However, from the viewpoint of antistatic properties, color resistance, and particularly transparency, It is preferable that it is a phosphonium ion represented by Formula (2). Examples of the alkali metal ion include lithium, sodium, potassium and the like.

Specific examples of R ² , R ³ , R ⁴ and R ^{5 in} the general formula (2) include methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, isobutyl, amyl, isoamyl. , Tertiary amyl, pentyl, hexyl, heptyl, 2-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like.
The number of carbon atoms of R ² , R ³ , R ⁴ and R ⁵ is preferably 2 to 8 from the viewpoints of antistatic properties, transparency and color resistance.

Specific examples of the compound represented by the general formula (1) include the following compound Nos. 1-No. However, the present invention is not limited to these compounds.

The antistatic agent of this invention can be manufactured by a well-known method, and there is no restriction | limiting in particular in a manufacturing method. For example, when X is an oxygen atom, the corresponding fatty acid and isethionic acid may be esterified and neutralized to give an alkali metal salt, ammonium salt or phosphonium salt. Further, when X is a —N (CH ₃ ) — group, the corresponding fatty acid and N-methyltaurine may be amidated and neutralized to obtain an alkali metal salt, ammonium salt or phosphonium salt.

  The antistatic agent for polycarbonate resin of the present invention may be added to the polycarbonate resin as it is, or may be added after impregnating the carrier. In particular, when the antistatic agent for polycarbonate resin of the present invention is liquid at room temperature, it is difficult to uniformly mix the polycarbonate resin with the polycarbonate resin. Therefore, it is preferable to impregnate the carrier before adding it to the polycarbonate resin.

When impregnating the carrier, it may be heated and mixed as it is, but if necessary, it may be diluted with an organic solvent, impregnated into the carrier, and then the solvent may be removed.
As the carrier, those known as synthetic resin fillers or inorganic fillers, or solid flame retardants or light stabilizers at room temperature can be used.

Examples of the carrier that can be used include calcium silicate powder, silica powder, talc powder, alumina powder, titanium oxide powder, or those obtained by surface chemical modification of these carriers, as well as flame retardants and antioxidants listed below. And solid ones.
Among these carriers, those obtained by chemically modifying the surface of the carrier are preferably used, and those obtained by chemically modifying the surface of the silica powder with a silane coupling agent or the like are more preferred.
The average particle diameter of these carriers is preferably 0.1 to 100 μm, and more preferably 0.5 to 50 μm.

The polycarbonate resin composition of the present invention is obtained by adding and blending the antistatic agent of the present invention to a polycarbonate resin. The polycarbonate resin referred to here includes not only a resin containing 100% polycarbonate but also a so-called polymer alloy obtained by mixing polycarbonate and another resin. Examples of such polymer alloys include polycarbonate / ABS resin, polycarbonate / AS resin, polycarbonate / rubber polymer compound, polycarbonate / ABS resin / rubber polymer compound, polycarbonate / polyethylene terephthalate, polycarbonate / polybutylene terephthalate, Examples include polycarbonate / ASA resin and polycarbonate / AES resin.
The ratio of the polycarbonate contained in these polymer alloys is preferably 50 to 98 parts by mass with respect to the mass of the polymer alloy.

  Examples of the above-mentioned 100% polycarbonate resin include a reaction product of one or more bisphenols and phosgene or a carbonic acid diester, or a reaction product obtained by transesterifying one or more bisphenols and a diphenyl carbonate. In general, those commercially available can be mentioned.

  Examples of bisphenols include hydroquinone, 4,4-dihydroxyphenyl, bis- (4-hydroxyphenyl) -alkane, bis- (4-hydroxyphenyl) -cycloalkane, bis- (4-hydroxyphenyl) -sulfide, Bis- (4-hydroxyphenyl) -ether, bis- (4-hydroxyphenyl) -ketone, bis- (4-hydroxyphenyl) -sulfone, bisphenolfluorene or their alkyl-substituted, aryl-substituted, halogen-substituted, etc. Is mentioned. These are used alone or in combination of two or more. The viscosity average molecular weight of the polycarbonate resin is preferably 10,000 to 100,000, and more preferably 10,000 to 50,000.

  Among such polycarbonates, it is preferable to use bisphenol A-based polycarbonates made from 2,2-bis- (4-hydroxyphenyl) propane, so-called bisphenol A, from the viewpoint of being readily available in the market.

  If the amount of the antistatic agent of the present invention to be blended in the polycarbonate resin is too large, the physical properties such as the mechanical strength of the polycarbonate resin may be lowered or it may be difficult to blend, and if it is small, the antistatic effect May become insufficient. Therefore, the content of the antistatic agent of the present invention is preferably 0.01 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin. Most preferably, it is 5-5 mass parts.

The blending method of the antistatic agent in the polycarbonate resin of the present invention is not particularly limited, and for example, it is mixed and kneaded by any commonly used method such as roll kneading, bumper kneading, extruder, kneader and the like. be able to.
Moreover, the antistatic agent of this invention can also be used as a coating type apply | coated to the surface of a polycarbonate resin molded product besides mix | blending with polycarbonate resin as what is called a kneading type | mold. When applying, it may be dissolved in various solvents and applied as a solution.

In order to improve the flame retardancy of the polycarbonate resin composition of the present invention, it is preferable to add and blend a flame retardant together with the antistatic agent of the present invention.
Examples of flame retardants that can be used in combination include tetrabromobisphenol A, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, and 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl). ) Halogen flame retardants such as propane, decabromodiphenyl oxide, hexabromocyclodecane, tetrabromophthalic anhydride, chlorinated polyethylene, chlorinated paraffin, perchlorocyclopentadecane, chlorendic acid, tetrachlorophthalic anhydride; ammonium phosphate, Tricresyl phosphate, triethyl phosphate, tris (β-chloroethyl) phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, cresyl diphenyl phosphate, xylenyl Phenyl phosphate, phenylene bis (diphenyl phosphate), phenylene bis (phenyl cresyl phosphate), phenylene bis (dicresyl phosphate), phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), Phosphorus flame retardants such as bisphenol A bis (dicresyl phosphate); red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, barium metaborate, zinc borate, aluminum hydroxide, magnesium hydroxide, nitrogenated guanidine, etc. Inorganic flame retardants.

但し、式中、Ｒ^６〜Ｒ^９はアリール基、Ｙはアリーレン基であり、ａ〜ｄは０若しくは１の数を表し、ｓは１〜５の数である。 Among the above-mentioned flame retardants, synthetic resins containing halogen-containing flame retardants such as halogen-based flame retardants and halogen-containing phosphorus-based flame retardants may generate dioxins during combustion. Flame retardants containing halogens tend to be avoided.
Some flame retardants, when used in combination with the antistatic composition of the present invention, may cause the synthetic resin to be colored by heat or the heat resistance to be lowered depending on the synthetic resin substrate. From such a viewpoint, it is preferable to use a phosphorus compound represented by the following general formula (3) as a flame retardant.

In the ^formula, R 6 to R ⁹ is an aryl group, Y is an arylene group, to d represents a number of 0 or 1, s is a number from 1 to 5.

R ^{6 to} R ⁹ in the general formula (3) are aryl groups, and these may be the same or different. Examples of aryl groups include phenyl, tolyl, benzyl, xylyl, phenethyl, styryl, trimethylphenyl, cumenyl, cumyl, hydrocinnamyl, cinnamyl, tetramethylphenyl, thymyl, carbacrylyl , Cuminyl group, neophyll group, xenyl group, benzhydryl group, triphenylmethyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, A decylphenyl group, an undecylphenyl group, a dodecylphenyl group, a naphthyl group, etc. are mentioned. In the present invention, among them, a phenyl group, a cresyl group, and a xylenyl group are preferable.

  The arylene group of Y is a residue obtained by removing a hydroxyl group from dihydric phenols. Examples of the dihydric phenols include resorcin, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, biphenol and the like.

  a to d represent a number of 0 or 1, and may be the same or different. s is an average value of repeating units and represents a number of 1 to 5.

The phosphorus compound represented by the general formula (3) can be produced by a known method such as the method disclosed in JP-A-59-202240.
Specific examples of the phosphorus compound represented by the general formula (3) include, for example, phenylene bis (diphenyl phosphate), phenylene bis (phenyl cresyl phosphate), phenylene bis (dicresyl phosphate), phenylene bis (dioxy). Silenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate) and the like.

  The content of these flame retardants varies depending on the type and use of the polycarbonate resin, but cannot be generally stated, but is preferably 0.5 to 30 parts by mass with respect to the polycarbonate resin, preferably 1 to 25 parts by mass. More preferably, it is most preferably 5 to 20 parts by mass.

In addition, the polycarbonate resin composition of the present invention is a known antioxidant, light stabilizer, ultraviolet absorber, fluoroolefin resin, other antistatic agent, and antifogging agent as long as the effects of the present invention are not hindered. , Lubricants, plasticizers, colorants, non-phosphorous flame retardants, flame retardant aids, antifungal agents, crystal nucleating agents, compatibilizers, antiblocking agents, foaming agents, inorganic electrolytes, fillers, fillers, pigments, fragrances In addition, other synthetic resin additives such as silicone oil and coupling agents may be contained, and conductive materials such as carbon fibers and stainless fibers may be further contained.
Among these, it is preferable to contain an antioxidant, a fluoroolefin resin, or a lubricant.

Examples of the antioxidant that can be used in the polycarbonate resin composition of the present invention include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant.
Examples of the phenolic antioxidant include 2,6-di-tert. -Butylphenol (hereinafter, tert.-butyl is abbreviated as t-butyl), 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2, 4-dimethyl-6-tert-butylphenol, 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4 ′ -Bis (2-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6) − Chlorylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,6-bis (2'-hydroxy-) 3'-t-butyl-5'-methylbenzyl) 4-methylphenol, 3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, 3- (4-hydroxy-3,5 -Di-t-butylphenyl) stearyl propionate, 3- (4-hydroxy-3,5-di-t-butylphenyl) oleyl propionate, 3- (4-hydroxy-3,5-di-t-butyl) Phenyl) dodecyl propionate, octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, tetrakis {3- (4-hydroxy-3,5- -T-butylphenyl) propionyloxymethyl} methane, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid glycerin monoester, 3- (4-hydroxy-3,5-di-t -Butylphenyl) propionic acid and glycerol monooleyl ether, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid butylene glycol ester, 3- (4-hydroxy-3,5- Di-t-butylphenyl) propionic acid thiodiglycol ester, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (2-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-α-dimethylamino-p -Cresol, 2,6-di-t-butyl-4 (N, N'-dimethylaminomethylphenol), bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, tris {(3, 5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl} isocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-tris (3 ′ , 5′-di-tert-butyl-4-hydroxybenzoyl) isocyanurate, bis {2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl} sulfide, 1,3,5 -Tris (4-di-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetraphthaloyl-di (2,6-dimethyl- -T-butyl-3-hydroxybenzyl sulfide), 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis (octylthio) -1,3,5-triazine, 2,2 -Thio- {diethyl-bis-3- (3,5-di-t-butyl-4-hydroxyphenyl)} propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4- Hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxy-benzyl-phosphate diester, bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, 3,9-bis [ 1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] Ndecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t -Butyl-4-hydroxybenzyl) benzene, bis {3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid} glycol ester, and the like.

  Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4-butylidenebis (3-methyl-6-tert-butylphenyldiisotridecyl) phosphite, Stearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2 , 6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 1,1,3-butyridine tris ( 3-methyl-6-tert-butylfe Rudiisotridecyl) phosphite, 2,2-propylidenebis (3-methyl-6-tert-butylphenyldiisotridecyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4-biphenylene -Diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9- And oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, and the like.

  Examples of the sulfur-based antioxidant include dioctyl thiodipropionate, didecyl thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate. , Distearyl-β, β′-thiodibutyrate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-decylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) pentaerythritol tetra Ester, (3-stearylthiopropionic acid) pentaerythritol tetraester, (3-oleylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) -4,4′-thiodi ( - methyl -5-t-butyl-4-phenol) ester, 2-mercaptobenzimidazole, 2-mercaptomethyl benzimidazole, 2-benzimidazole disulfide, dilauryl sulfide, Ami Lucio glycol.

  Since the content of these antioxidants varies depending on the polycarbonate resin used as the base material, it cannot be generally specified, but is preferably about 0.001 to 15 parts by mass with respect to 100 parts by mass of the polycarbonate resin base material. 0.005 to 10 parts by mass is more preferable, and 0.01 to 5 parts by mass is most preferable.

  The polycarbonate resin composition of the present invention preferably contains a fluoroolefin resin. Since the synthetic resin composition containing the fluoroolefin resin is prevented from dripping at the time of melting, it is difficult to ignite or burn when a fire occurs. Since the content of the fluoroolefin resin varies depending on the synthetic resin used as a base material and the application, it cannot be generally stated, but it is generally 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin base. Preferably, it is 0.1 to 2 parts by mass, and most preferably 0.5 to 1.5 parts by mass.

  The fluoroolefin resin here is a polymer containing a fluoroethylene structure, and includes, for example, a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene and fluorine. And a copolymer with no ethylene monomer.

  Among these, it is preferable to use polytetrafluoroethylene (PTFE). The average molecular weight of PTFE is preferably 500,000 or more, particularly preferably 500,000 to 10,000,000. Specific examples of PTFE include Teflon (registered trademark) 6-J (manufactured by Mitsui DuPont Fluorochemicals), Polyflon D-1, Polyflon FA-100, Polyflon F-103, Polyflon F-201, and Polyflon MPA (Daikin Industries). , CD076 (manufactured by Asahi IC Fluoropolymers), Algoflon F5 (manufactured by Montefluos), and the like.

Examples of the lubricant that can be used in the polycarbonate resin composition of the present invention include hydrocarbon lubricants such as liquid paraffin, paraffin wax, and polyethylene wax; aliphatic lubricants such as stearyl alcohol, stearic acid, and 12-hydroxystearic acid; stearin Amide lubricants such as acid amide, oleic acid amide, erucic acid amide, methylenebis stearic acid amide, ethylene stearic acid amide; calcium stearate, zinc stearate, magnesium stearate, lead stearate, aluminum stearate, barium stearate, Metal soap lubricants such as barium stearate / zinc stearate complex, zinc stearate / calcium stearate complex; hardened oil and fat, glycerin monostearate, butyl stearate, pentae Sri tall stearate, include ester lubricant such as stearyl stearate.
Since the content of these lubricants varies depending on the synthetic resin used as the base material, it cannot be generally stated, but is generally preferably 0.001 to 15 parts by mass with respect to 100 parts by mass of the synthetic resin base material. It is more preferable that it is 005-10 mass parts, and it is most preferable that it is 0.01-5 mass parts.

Examples of ultraviolet absorbers that can be used in the polycarbonate resin composition of the present invention include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and other ultraviolet absorbers.
Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- {2' -Hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl} benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) Nzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl ) -5′-methylphenyl} benzotriazole, 2,2-methylenebis {4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol}, 2- (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole and the like.

  Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 ′. -Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) Methane) and the like.

  Examples of other ultraviolet absorbers include salicylates such as phenyl salicylate, 4-t-butylphenyl salicylate, 4-octylphenyl salicylate; ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2- Examples include ultraviolet absorbers such as cyanoacrylates such as cyano-3,3-diphenyl acrylate; oxalic acids such as 2-ethoxy-2′-ethyl oxalic acid bisanilide.

  The content of these ultraviolet absorbers varies depending on the synthetic resin used as the base material, and thus cannot be generally stated, but is generally preferably 0.001 to 15 parts by mass with respect to 100 parts by mass of the synthetic resin base material. The amount is more preferably 0.005 to 10 parts by mass, and most preferably 0.01 to 5 parts by mass.

  Examples of the hindered amine light stabilizer that can be used in the polycarbonate resin composition of the present invention include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6). , 6-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl)- 2-n-butyl malonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6) -Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (mixed-2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2 3,4-butanetetracarboxylate, (mixed-1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed- {2 , 2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) Diethyl} -1,2,3,4-butanetetracarboxylate, mixed- {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3 , 9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethyl} -1,2,3,4-butanetetracarboxylate, poly {6- (1,1,3,3) , -Tetramethylbutyl) imino-1,3 -Triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}, Dimethyl succinate / 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol polymer, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6 Examples thereof include 6-pentamethyl-4-piperidyl methacrylate and ethylene bis (2,2,6,6-tetramethyl-3-oxa-4-piperidine).

  Other light stabilizers that can be used in the polycarbonate resin composition of the present invention include, for example, {2,2′-thiobis (4-tert-octylphenolate)}-2-ethylhexylamine nickel (II), nickel dibutyldithio Carbamate, {2,2′-thiobis (4-t-octylphenolate)}-2-butylamine nickel (II), nickel bis (octylphenyl) sulfide, 3,5-di-t-butyl-4-hydroxybenzyl Examples thereof include nickel-based light stabilizers such as a phosphoric acid monoethylate nickel complex; 2,4-di-t-butylphenyl-3,5′-di-t-butyl-4′-hydroxybenzoate and the like.

  The content of these light stabilizers varies depending on the synthetic resin used as the base material, and thus cannot be said unconditionally, but is generally preferably 0.001 to 15 parts by mass with respect to 100 parts by mass of the synthetic resin base material. The amount is more preferably 0.005 to 10 parts by mass, and most preferably 0.01 to 5 parts by mass.

  Examples of other antistatic agents that can be used in the polycarbonate resin composition of the present invention include glycerin mono fatty acid ester, polyglycerin fatty acid ester, diethanolamine fatty acid amide, polyalkylene glycol alkyl ether, N-alkyl ammonium chloride, and phosphonium alkylbenzene sulfonate. Although salt etc. are mentioned, since these are inferior in heat resistance, it is preferable to reduce the usage-amount and it is most preferable to avoid use.

  Examples of other additives that can be used in the polycarbonate resin composition of the present invention include dibenzylidene sorbitol, bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and hydroxy-di (t-butylbenzoic acid). ) Nucleating agents such as aluminum, sodium bis (4-t-butylphenyl) phosphate, sodium 2,2-methylenebis (4,6-di-t-butylphenyl) phosphate; phthalates, dibasic acids Plasticizers such as ester, chlorinated paraffin, polyester, epoxidized ester, phosphate ester, trimellitic acid ester; metal soap, organotin, organolead, phosphite, epoxide, β-diketone, polyol, perchlorate, Hydrotalcite, stabilizers for zeolitization, titanium compounds, etc. Coloring material, calcium silicate powder, silica powder, talc powder, mica powder, alumina powder, titanium oxide powder, fillers such as glass flakes and the like.

Hereinafter, the present invention will be specifically described by way of examples, and examples and comparative examples. However, the present invention is not limited to these examples.
In the following examples and the like,% and ppm are based on mass unless otherwise specified.

[Production Example 1] Compound No. 1 Synthesis of No. 1 6.4 g (0.032 mol) of lauric acid and 5.72 g (0.032 mol) of a 70% aqueous solution of isethionic acid were added to 100 ml of toluene, followed by reflux dehydration for 8 hours. After cooling to room temperature, an aqueous solution in which 1.26 g of sodium hydroxide was dissolved in 30 ml of water was added to the reaction system, and the mixture was stirred at 50 ° C. for 3 hours.
Thereafter, 11.8 g (0.032 mol) of tetrabutylphosphonium bromide was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 100 ml of water was added, and the mixture was extracted with ethyl acetate. 1 was obtained.

[Production Example 2] Compound No. Synthesis of 13 8 g (0.029 mol) of sodium lauroylmethyltaurine and 9.8 g (0.029 mol) of tetrabutylphosphonium were added to 100 ml of water and stirred at 80 ° C. for 2 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and 15.5 g of the following compound No. 13 was obtained.

[Examples 1 and 2, Comparative Examples 1 and 2]
Under the following conditions, Compound No. 1 and compound no. A test piece was prepared using 13 and performance evaluation was performed under the following conditions. The results are shown in Table 1. Further, as comparative examples, the case where no antistatic agent was used and the case where the following comparative compound-1 was used were similarly tested and evaluated.

1. Test piece preparation <Polycarbonate resin composition preparation>
3 parts by weight of antistatic agent dried at 110 ° C. for 6 hours is added to 100 parts by weight of polycarbonate resin (Iupilon S-3000: trade name manufactured by Mitsubishi Engineering Plastics Co., Ltd.) dried at 110 ° C. for 6 hours. To obtain a polycarbonate resin composition.
The obtained polycarbonate resin composition was melt-kneaded at 260 ° C. and formed into pellets using a single screw extruder (Laboplast Mill μ2D25W: trade name, manufactured by Toyo Seiki Seisakusho Co., Ltd.).

<Preparation of test piece by injection molding>
The pellets were molded by a vertical injection molding machine (SA-60-52-CP: trade name of Yamashiro Seiki Seisakusho Co., Ltd.) under the following processing conditions to obtain test pieces of 100 mm × 100 mm × 2 mm.
Temperature: 270 ° C
Mold temperature: 80 ℃

2. Evaluation Method <Surface Specific Resistance Value (SR Value)>
Immediately after molding the test piece, it was stored at 25 ° C. under a humidity of 60%, and applied with an R8340 resistance meter (trade name, manufactured by Advantest) under the same atmosphere after 1 day and 1 week. The surface resistivity (Ω / □) was measured under the conditions of a voltage of 500 V and an application time of 1 minute. The measurement was performed on five points on the test piece, and the average value was obtained.

<Transparency evaluation>
Using haze guard II (trade name, manufactured by Toyo Seiki Seisakusho Co., Ltd.), haze values were measured at five points on the test piece, and the average value was obtained.

<Evaluation of coloring resistance>
Using a color difference meter SC-P (trade name, manufactured by Suga Test Instruments Co., Ltd.), yellowness (YI) was measured at five points on the test piece, and the average value was obtained.

The evaluation results are shown in Table 1 below.

As is clear from Table 1, since the surface specific resistance of the polycarbonate resin of Comparative Example 1 is higher than the surface specific resistances of Examples 1, 2 and Comparative Example 2, the antistatic of the polycarbonate resin to which no antistatic agent is added. It was confirmed that the property is low.
Further, the polycarbonate resin of Comparative Example 2 to which Comparative Compound-1 was added as an antistatic agent was confirmed to have a low surface specific resistance and an improved antistatic property. Since the resistance doubled, it was confirmed that the antistatic effect was inferior in sustainability. Furthermore, since the polycarbonate resin of Comparative Example 2 has a high yellowness, it was confirmed that it was inferior in coloring resistance.
In contrast to these results, the polycarbonate resin composition of the present invention has little change in the surface resistivity, and also has a low haze value and yellowness, so that the antistatic property, the durability of the antistatic effect, the transparency and the anti-coloring property It was confirmed that it was excellent in all properties.

  The polycarbonate resin composition of the present invention not only has a good antistatic effect, but also has excellent transparency and anti-coloring properties. Therefore, electrical and electronic members, medical members, optical members, and other various types. It is useful as a molded product in a wide range of fields.

Claims (2)

An antistatic agent for polycarbonate resin, comprising a compound represented by the following general formula (1);

However, ^{R 1} in the formula (1) is an alkyl group having 1 to 30 carbon atoms, X is an oxygen atom or -N (CH ₃₎ - is a group, M is an alkali metal ion, an ammonium ion, or the following general A phosphonium ion represented by formula (2);

However, ^{R 2,} R 3, ^{R 4} and ^{R 5} in formula (2) are each independently an alkyl group having 1 to 18 carbon atoms.   A polycarbonate resin composition comprising 0.01 to 20 parts by mass of the antistatic agent for polycarbonate resin according to claim 1 with respect to 100 parts by mass of the polycarbonate resin.