JP2019167468A - Polycarbonate resin composition, its molded product and its production method - Google Patents

Abstract

To provide a polycarbonate resin composition having various kinds of excellent properties provided with a polysiloxane structure, without damaging mechanical characteristics such as impact resistance that the polycarbonate resin intrinsically has, and having especially excellent dust resistance and cleaning property of a sebum, and having fire retardancy.SOLUTION: A polycarbonate resin composition in which a polycarbonate resin, a polysiloxane compound expressed by a formula (1) in the range of 0.1 mass% or larger and 5 mass% or smaller relative to the polycarbonate resin, and a sulfonate in the range of 0.01 mass% or larger and 5 mass% or smaller relative to the polycarbonate resin are blended, the polysiloxane compound expressed by the formula (1) has a number average molecular weight of 900 or larger and 120,000 or smaller.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate-based resin composition, and more specifically, a polycarbonate-based resin composition having improved dustproofness, detergency such as sebum dirt, and flame retardancy without reducing the impact resistance of the polycarbonate-based resin. The present invention relates to a molded product and a manufacturing method thereof.

  Polycarbonate resins are widely used in various fields such as OA (office automation) equipment, information / communication equipment, electrical / electronic equipment, automobile field, and architecture field due to their excellent impact resistance, heat resistance, and electrical characteristics. ing. Polycarbonate resins are generally excellent in flame retardancy, but their molded products are required to have a high degree of flame retardancy and are improved by the addition of various flame retardants. In addition, polycarbonate resin has a large surface resistivity, and the molded product causes dust to adhere to the surface due to static electricity induced by contact or friction, and electronic devices such as ATMs and POS terminals that are touched by an unspecified number of people. In equipment and the like, it is difficult to adhere dust, and cleaning properties such as sebum dirt are required. In order to meet these demands, it is desired to provide antistatic properties and cleaning properties such as sebum stains while maintaining the mechanical properties and the like inherent to polycarbonate resins. That is, there is a need for a resin composition that is excellent in impact resistance and flame retardancy, and that can provide a molded product having good antistatic properties and cleanability.

  In order to modify the polycarbonate resin, it is known to add a polysiloxane compound to the polycarbonate resin to obtain a polysiloxane-modified polycarbonate. For example, technologies that impart flame retardancy to polycarbonate resins without generating harmful gases during combustion and improve moldability (Patent Documents 1 and 2), and give molded articles with antifouling properties (patents) Reference 3). These resin compositions sometimes have insufficient flame retardancy and moldability of the resin component itself.

  Further, as a method for preventing the adhesion of dirt on the polycarbonate resin molded product, a method for preventing charging by blending an ionic surfactant such as an alkali metal sulfonate or phosphonium sulfonate is known. Such antistatic performance by the ionic surfactant is manifested by precipitation of a part of the surfactant on the surface from the molded product of the resin composition to which the surfactant is added. However, in a molded article of a polycarbonate resin composition in which a compound having a low surface tension such as a polysiloxane compound is added to a polycarbonate resin, the polysiloxane compound is deposited on the surfactant deposited on the surface of the molded article. The antistatic performance is significantly reduced.

  Incidentally, in order to produce a polysiloxane-modified polycarbonate, generally, (1) a method of directly kneading a polysiloxane compound and a polycarbonate, or (2) a reactive functional group when obtaining a polycarbonate by a polycondensation reaction. A method of producing a polysiloxane-modified polycarbonate by adding a polysiloxane compound having a polysiloxane compound as a reaction component to a reaction system and chemically bonding the polysiloxane compound to a polycarbonate to be produced is used.

  However, although the method (1) is a simple method, only a part of the polysiloxane compound chemically reacts and a large amount of unreacted polysiloxane compound is mixed. When the resulting polysiloxane-modified polycarbonate is used as a molded article, there is a problem that a so-called bleedout phenomenon occurs in which the polysiloxane compound oozes out on the surface of the molded article. Furthermore, as described above, precipitation of the surfactant on the surface of the molded product is hindered, and the antistatic performance is remarkably lowered. The method (2) also has problems such as difficulty in obtaining the target polysiloxane-modified polycarbonate due to the problem of reactivity during polycondensation of carbonate. For this reason, increasing the use ratio of the polysiloxane compound with respect to the monomer for molding the polycarbonate, in order to obtain a polysiloxane-modified polycarbonate having the desired modification effect, decreases the degree of polymerization of the resulting polycarbonate. Also, there is a problem that the properties of polycarbonate are impaired.

  The present inventors have provided a polysiloxane-modified polylactic acid-based composition (Patent Documents 4 and 5) or a polycarbonate resin composition having mechanical strength such as flame retardancy and impact resistance and imparting bleed resistance. (Patent Document 6) has already been disclosed. However, these resin compositions have not been able to obtain a resin molded product having antistatic properties and having antifouling properties, dustproof properties and cleaning properties.

  In addition, a technique (Patent Documents 7-9) for improving the wear resistance, stability at high temperature use, etc. is disclosed for polysiloxane-modified polyester.

JP 2002-12746 A JP 2002-12755 A Japanese Patent Laid-Open No. 03-205426 Patent No. 5573833 JP 2012-072351 A JP 2004-035726 A JP 09-316185 A JP-A-10-95902 Japanese Patent Laid-open No. 10-100188

  The object of the present invention is to suppress the adhesion of dust and the like, that is, to prevent dust and the like, and to improve the washability and flame retardance of the attached sebum, etc. without reducing the impact resistance in the molded article of the polycarbonate resin. An object of the present invention is to provide a polycarbonate resin composition that can be produced, a molded product thereof, and a production method thereof.

  The present inventor has intensively studied the improvement of the impact resistance, dust resistance, cleaning properties, flame retardancy and the like of the polycarbonate resin. As a result, the molecular weight and molecular structure of a siloxane compound having a specific structure are selected and used, and a specific sulfonate is melt-kneaded with a polycarbonate resin to maintain a high level of impact resistance while bleeding. It was found that by controlling out-out and imparting antistatic performance, a molded product having excellent dustproofness and sebum cleansing properties and significantly improved flame retardancy can be obtained. Furthermore, it has been found that the flame retardancy level can be further improved by selectively using a specific fluororesin, and the present invention has been completed.

  That is, the polycarbonate resin composition of the present invention includes a polycarbonate resin, a polysiloxane compound represented by the formula (1) in a range of 0.1% by mass to 5% by mass with respect to the polycarbonate resin, A sulfonate represented by the formula (2) in a range of 0.01% by mass to 5% by mass with respect to the polycarbonate resin is blended, and the polysiloxane compound represented by the formula (1) is a number average. The present invention relates to a polycarbonate resin composition having a molecular weight of 900 or more and 120,000 or less.

(In the formula, R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are an alkyl group, alkenyl group, aryl group, aralkyl group, alkylaryl group, or — (CH ₂ ) _α- NH—C having 18 or less carbon atoms. ₆ H ₅ (α is an integer of 1 to 8), which may be the same or different from each other, may be wholly or partially substituted with a halogen atom, and R ₈ and R ₉ are divalent organic groups. M and p are numerical values of m ≧ 0 and p> 0, respectively.)
^{_{R 10 -SO 3 M + (2}} )
(Wherein R ₁₀ represents an alkyl group having 1 to 40 carbon atoms, an aralkyl group having 6 to 40 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and M ⁺ represents a metal ion or an organic onium ion.)
The molded product of the polycarbonate-type resin composition of this invention is related with the molded product shape | molded by the said polycarbonate-type resin composition.

  The method for producing a polycarbonate resin composition of the present invention comprises a shearing action of a polycarbonate resin in a molten state, a polysiloxane compound represented by Formula (1), and a sulfonate represented by Formula (2). It is related with the manufacturing method of the polycarbonate-type resin composition which mixes and stirs.

  According to the polycarbonate resin composition and the method for producing the same of the present invention, the polycarbonate resin acts on the polysiloxane compound represented by the highly polar formula (1), and the polycarbonate resin and the polysiloxane compound are efficiently chemically treated. Since it interacts by a bond or a hydrogen bond, a polycarbonate resin composition can be advantageously obtained. For this reason, in the molded article of the polycarbonate resin composition of the present invention, since the precipitation of the polysiloxane compound on the surface of the molded article is suppressed, the antistatic performance by the sulfonate is maintained and the inherent resistance of the polycarbonate resin. It does not impair mechanical properties such as impact properties, has various excellent properties given by the polysiloxane structure, has excellent antifouling properties and cleansing properties such as sebum, and has flame retardancy.

  The polycarbonate resin composition of the present invention includes a polycarbonate resin, a polysiloxane compound represented by the formula (1) in the range of 0.1% by mass to 5% by mass with respect to the polycarbonate resin, and the polycarbonate The polysulfonate compound represented by the formula (1) is blended with the sulfonate represented by the formula (2) in the range of 0.01% by mass or more and 5% by mass or less with respect to the resin based on the number average molecular weight. It is 900 or more and 120,000 or less.

(In the formula, R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are an alkyl group, alkenyl group, aryl group, aralkyl group, alkylaryl group or — (CH ₂ ) α-NH—C having 18 or less carbon atoms. ₆ H ₅ (α is an integer of 1 to 8), which may be the same or different from each other, may be wholly or partially substituted with a halogen atom, and R ₈ and R ₉ are divalent organic groups. M and p are numerical values of m ≧ 0 and p> 0, respectively.)
R ₁₀ —SO ₃ M ⁺ (2)
_{(Wherein, R 10} represents an alkyl group, an aralkyl group having 6 to 40 carbon atoms or an aryl group having a carbon number of 6 to 40,, ^{M +} is a metal ion or an organic onium carbon 1-40.)
The polycarbonate-based resin may be any one as long as the monomer unit is joined by a carbonate group (—O— (CO) —O—), but one having an aromatic group in the monomer unit. preferable. As the aromatic carbonate resin, polymers obtained by a phosgene method in which various dihydroxydiaryl compounds having a carbonate group are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted are used. Representative examples include polycarbonates made from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1 1-bis (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3, Dihydroxy diaryl sulfoxides such as 3'-dimethyldiphenyl sulfoxide, dihydroxy diaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Reel sulfone, and the like. These are used singly or in combination of two or more, but it is preferable that they are not substituted with a halogen atom since generation of the halogen-containing gas can be prevented during combustion. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-trimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  The number average molecular weight of the polycarbonate-based resin is preferably 10,000 or more and 100,000 or less, more preferably 15,000 or more and 50,000 or less, and still more preferably 20,000 or more and 40,000 or less. When the polycarbonate-based resin having such an average molecular weight is produced, the molecular weight can be adjusted by using a molecular weight regulator, a catalyst or the like as necessary. A polycarbonate resin having such a molecular weight has excellent mechanical properties such as impact resistance.

The polysiloxane compound represented by the formula (1) has a side chain containing a diamino group. Here, the side chain containing a diamino group means an amino group (—NH ₂ ) at the end of the side chain and an imino group (—NH—) in the main chain of the side chain.

In the formula, R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each an alkyl group, alkenyl group, aryl group, aralkyl group, alkylaryl group or — (CH ₂ ) _α -NH—C ₆ having 18 or less carbon atoms. H ₅ (α is an integer of 1 to 8), which may be the same or different from each other, and may be wholly or partially substituted with halogen atoms such as fluorine and chlorine. The alkyl group and alkenyl group are those having 18 or less carbon atoms. - In the _{(CH 2) α -NH-C} 6 H 5, α may be any integer of 1 to 8.

R ₈ and R ₉ may be a divalent organic group constituting a side chain containing a diamino group of the polysiloxane compound of the formula (1), and specific examples include an alkenyl group.

  p represents a numerical value of p> 0, and is appropriately selected in relation to the diamino group, and m represents a numerical value of m ≧ 0. p and m are appropriately selected in relation to the number average molecular weight of the polysiloxane compound.

  The polysiloxane compound represented by the formula (1) has a number average molecular weight of 900 or more and 120,000 or less. Preferably they are 900 or more and 30000 or less, More preferably, they are 900 or more and 8000 or less. By having such a molecular weight, it can be efficiently bonded to the polycarbonate-based resin and can have an interaction through a hydrogen bond, and can impart a dustproof property and a cleaning property to the molded product.

In the sulfonate represented by the formula (2), R ₁₀ represents an alkyl group having 1 to 40 carbon atoms, an aralkyl group having 6 to 40 carbon atoms, or an aryl group having 6 to 40 carbon atoms. As a C1-C40 alkyl group, a dodecyl group, a decyl group, a butyl group, an ethyl group etc. can be mentioned, for example, A dodecyl group and a decyl group are especially preferable. Examples of the aralkyl group having 6 to 40 carbon atoms include a benzyl group and a phenethyl group, and a benzyl group is particularly preferable. Examples of the aryl group having 6 to 40 carbon atoms include a phenyl group, a naphthyl group, a tolyl group, and a dodecylphenyl group, and a dodecylphenyl group is particularly preferable. In these alkyl group, aralkyl group and aryl group, part of the hydrogen atoms may be substituted with a halogen atom such as a fluorine atom, and the aralkyl group and aryl group may contain a hetero atom. Specific examples of the sulfonic acid component include dodecylbenzenesulfonic acid and perfluoroalkanesulfonic acid.

In the formula, examples of the metal component of the metal ion in M ⁺ include alkali metals and alkaline earth metals such as potassium, sodium, cesium, and rubidium, and examples of the onium component of the organic onium ion include phosphonium, ammonium, and the like. Is mentioned. Of these, sodium, potassium, phosphonium, and ammonium are preferable, and sodium is particularly preferable. These can be used alone or in combination of two or more.

  The fiber-forming fluorine-containing polymer that may be blended in the polycarbonate resin composition has a function of forming the polycarbonate resin into a fibril structure. By blending such a fluorine-containing polymer, the drip phenomenon at the time of combustion can be suppressed. Examples of the fiber-forming fluoropolymer include tetrafluoroethylene copolymers such as polytetrafluoroethylene and tetrafluoroethylene-hexafluoropropylene copolymers, partially fluorinated polymers as shown in US Pat. No. 4,379,910, Examples include polycarbonates produced from fluorinated diphenols.

  The fiber-forming fluorine-containing polymer can suppress drip at the time of combustion of the polycarbonate resin by being blended in the range of 0.05% by mass or more and 1% by mass or less with respect to the polycarbonate resin.

  In addition to the polysiloxane compound represented by the above formula (1), the polycarbonate-based resin composition is blended with a polysiloxane compound having no diamino group and other resins within a range not impairing the effects of the present invention. It may be. In addition, various heat stabilizers, antioxidants, colorants, fluorescent brighteners, fillers, mold release agents, softeners, antistatic agents and other additives, impact modifiers, and other polymers are blended. It may be.

  Examples of the heat stabilizer include hydrogen sulfate metal salts such as sodium hydrogen sulfate, potassium hydrogen sulfate, and lithium hydrogen sulfate, and metal sulfate salts such as aluminum sulfate. These heat stabilizers are used in the range of 0% by mass to 0.5% by mass with respect to 100% by mass of the polycarbonate resin.

  Examples of the filler include glass fiber, glass bead, glass flake, carbon fiber, talc powder, clay powder, mica, potassium titanate whisker, wollastonite powder, silica powder, and aluminum borate whisker.

  Examples of impact modifiers include acrylic elastomers, polycarbonate elastomers, core-shell type methyl methacrylate / butadiene / styrene copolymers, methyl methacrylate / acrylonitrile / styrene copolymers, ethylene / propylene rubbers, ethylene / propylene / diene systems. Rubber etc. can be mentioned.

  Examples of other polymers include polyesters such as polyethylene terephthalate and polybutylene terephthalate; polystyrene, high-impact polystyrene, acrylonitrile / styrene copolymer and its modified acrylic rubber, acrylonitrile / butadiene / styrene copolymer, acrylonitrile / ethylene- Examples thereof include styrene polymers such as propylene-diene rubber (EPDM) / styrene copolymer, polypropylene, and polymers usually used after being alloyed with polycarbonate.

  The method for producing a polycarbonate resin composition of the present invention comprises a polycarbonate resin in a molten state, a polysiloxane compound represented by formula (1), a sulfonate salt represented by formula (2), and if necessary. And a method of mixing and stirring the fiber-forming fluorine-containing polymer by applying a shearing action. As a method for heating the polycarbonate resin to the melting temperature or higher, the polycarbonate resin is supplied to an extruder in which the cylinder temperature is set to a temperature higher than the melting temperature, for example, 250 ° C. or higher. After making a polycarbonate-type resin into a molten state, the polysiloxane compound represented by Formula (1) and the sulfonate represented by Formula (2) are supplied to the extruder in a predetermined amount. A resin composition can be produced by rotating a screw at a predetermined speed and applying a shearing force to the reaction product and kneading. Since the polycarbonate-based resin is in a molten state, a graft polymer in which the polysiloxane compound is efficiently bonded, or a state in which the polysiloxane compound and the polycarbonate-based resin interact with each other through hydrogen bonding can be obtained.

  The molded article of the present invention is obtained by molding a polycarbonate resin composition, and the polycarbonate resin composition can be produced using an injection molding method, an injection / compression molding method, or the like. As molded articles, it is applied to OA (office automation) equipment, information / communication equipment, electrical / electronic equipment such as electrical appliances, automobile field, construction field, especially electronic equipment that can be operated by an unspecified number of people, For example, components such as an ATM terminal, a POS terminal, a composite copying machine, a server, a smartphone terminal, and a tablet terminal can be preferably cited. These parts have excellent flame retardancy and mechanical strength, and are highly dustproof and cleanable.

The polycarbonate-type resin composition of this invention is demonstrated concretely.
In the following examples and comparative examples, the materials used are as follows.
1. PC: Polycarbonate: Idemitsu Kosan Co., Ltd. Toughlon A2200 (mass average molecular weight 38000, number average molecular weight 16000)
2. B: Sulfonate: Sodium linear alkylbenzene sulfonate Wako Pure Chemical Industries, Ltd. 3. The following was used as the amino group-containing polysiloxane compound (C).

C1: Side chain diamino type polysiloxane compound: FZ-3705 manufactured by Toray Dow Corning Co., Ltd. (viscosity (25 ° C.): 230 mm ² / s, amino equivalent 4000 (g / mol))
C2: Side chain monoamino polysiloxane compound: KF-865 manufactured by Shin-Etsu Chemical Co., Ltd. (viscosity (25 ° C.): 110 mm ² / s, amino equivalent 5000 (g / mol))
In addition, the polysiloxane compound which has an amino group can be manufactured according to description of a silicone handbook (Nikkan Kogyo Shimbun, Inc. p.165) etc. The amino group-containing polysiloxane compound having an amino group in the side chain is synthesized using a siloxane oligomer obtained by hydrolysis of aminoalkylmethyldimethoxysilane, a cyclic siloxane, and a basic catalyst. Further, by using bis (aminopropyl) tetramethyldisiloxane, a cyclic siloxane, and a basic catalyst, a polysiloxane compound having amino groups at both ends can be obtained. Furthermore, depending on the molecular weight of the siloxane compound component and the proportion of the M units and D units constituting the siloxane compound, an appropriate amount of the partial hydrolysis-condensation product of diorganodichlorosilane is dissolved in an organic solvent, and water is added to add water. A decomposed and partially condensed siloxane compound is formed, and triorganomonochlorosilane is further added and reacted. After the polymerization is completed, the solvent is separated by distillation or the like to obtain a polysiloxane compound.
4). D: Epoxy group-containing polysiloxane compound: SF-8411 manufactured by Toray Dow Corning Co., Ltd. (viscosity (25 ° C.): 8000 mm ² / s, epoxy equivalent 3000 (g / mol))
5. E: Polydimethylsiloxane compound: Shin-Etsu Chemical Co., Ltd. KF96 (viscosity: 200 [mm ² / s] (25 ° C.))
6). F: Fiber-forming fluorine-containing polymer: Polytetrafluoroethylene Daikin Polyflon FA-500
[Example 1]
The polycarbonate (PC) and the side chain diamino type polysiloxane compound (C1) were placed in a continuous kneading extruder (KCK, KCK80X2-35VVEX (7)) with a cylinder temperature set at 280 ° C. ) Was supplied from the hopper port, and the side chain diamino polysiloxane compound (C1) was supplied from the vent port. At this time, sodium alkylbenzenesulfonate (B) in a proportion of 3% by mass with respect to the mass of the polycarbonate (PC), and side chain diamino type polysiloxane compound (C1) in an amount of 1% by mass with respect to the mass of the polycarbonate. And the total amount supplied per hour was 6 kg. Then, the screw was rotated at 32 rpm, and these materials were kneaded under melt shearing, and then extruded into a strand from the die port of the extruder, which was cooled in water and cut into pellets. The obtained polycarbonate-based resin composition was dried at 120 ° C. for 4 hours, and then a cylinder temperature: 280 ° C. and a mold setting temperature: 70 using a 20 t injection molding machine (EC20P-0.4A manufactured by Toshiba Machine). A test piece was prepared by molding at a temperature of ° C.

About the obtained test piece, the flame retardance evaluation UL94V, the oxygen index, the measurement of Charpy impact strength, the measurement of the surface resistivity and the detergency, and the bleed state were observed by the following methods, and the properties were examined. .
[Flame retardancy evaluation UL94V]
The flame retardancy evaluation UL94V is a UL94 test (equipment defined by Underwriters Laboratories) after leaving a test piece (125 mm x 13 mm x 1.6 mm) in a constant temperature room at a temperature of 23 ° C and a humidity of 50% for 48 hours. In accordance with the combustibility test of plastic materials for parts. UL94V is a method for evaluating flame retardance from the afterflame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically. It is divided into.

-When taking combustion forms other than the above classification, it was classified as notV-2. When the evaluation results are arranged in order of good flame retardancy, V-0, V-1, and (V-2 or notV-2) are obtained.
The afterflame time is the length of time that the test piece after the ignition source is kept away from flaming combustion, t1 is the afterflame time after the first flame contact, and t2 is the second time The after-flame time after flame contact, t3, is the after glow (flameless combustion) time after the second flame contact. The second flame contact is performed by indirect flame for 10 seconds with a burner immediately after the first flame contact, after the flame has disappeared.
-Ignition of cotton by drip is determined by whether the marking cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece.
[Oxygen index]
The oxygen index was measured according to JIS-K-7201 for a test piece (125 mm × 6 mm × 3.0 mm). The results are shown in Table 2.
[Charpy impact strength]
The Charpy impact strength was measured according to ISO 179 by notching a test piece (10 mm × 80 mm × 4.0 mm). The results are shown in Table 2.
[Surface resistivity]
The surface resistivity was measured according to ASTM D257 for a test piece (70 mm × 70 mm × 2.0 mm). The results are shown in Table 2.
[Detergency]
Detergency was measured as follows using a test piece (70 mm × 70 mm × 2.0 mm) with reference to the JISL1919C method. In the center of the test piece, oleic acid 30 mg or artificial sebum * 10 mg colored with a red dye as artificial dirt was applied as uniformly as possible to a circle with a diameter of about 40 mm. Wiping operation was performed once or three times for artificial dirt on the surface of the test piece using a towel sprayed with water. After the wiping operation, the artificial dirt remaining on the surface of the test piece was wiped off with a tissue paper attached to the surface of a disk having a diameter of 20 mm, the whiteness of the tissue paper was measured with a color difference meter, and the removal rate was calculated by the following equation. The results are shown in Table 2.
Composition of artificial sebum Triolein 23%, paraffin wax 21%, monoolein 6%, squalene 10%, oleic acid 9%, stearic acid 9%, linoleic acid 9%, palmitic acid 9%, cholesterol 2%, liquid paraffin 2%
・ Removal rate (%) = (A−B) / (Whiteness of tissue−B) × 100
A: Whiteness of the tissue paper after the wiping operation of the artificial dirt remaining on the test piece after the wiping operation with the artificial dirt towel
B: Whiteness of the tissue paper that was wiped with artificial dirt on the test piece without wiping with artificial dirt towels
[Bleed]
The bleed condition was determined by observing the surface of the test piece with the naked eye and a microscope after heating the test piece in a 100 ° C. hot air circulation oven for 100 hours, and evaluating the degree of oozing on the surface of the test piece according to the following criteria. The results are shown in Table 2.
○: No surface exudation Δ: Slight exudation on the surface ×: Exudation on the surface is remarkable.
[Examples 2-6, Comparative Examples 1-8]
Next, linear alkylbenzene sulfonate sodium (B), side chain diamino type polysiloxane compound (C1), side chain monoamino type polysiloxane compound (C2), epoxy group-containing polysiloxane compound (D), polysiloxane compound (E ) And a fiber-forming fluoropolymer (F) with respect to the polycarbonate (PC) in the same manner as in Example 1 except that they were blended in the blending amounts shown in Tables 2 to 4, Evaluation was conducted and the properties thereof were examined. The results are shown in Tables 2-4.

From the result of Examples 1-3, the polycarbonate composition which mix | blended 1-5 mass% of linear alkylbenzenesulfonic acid sodium (B) 3 mass% and the side chain diamino type polysiloxane compound (C1) with polycarbonate (PC). Oleic acid and artificial sebum, which are highly flame retardant with an oxygen index of 30 or more, have excellent impact strength, have a surface resistivity of 10 ¹⁵ Ω or less, have excellent dust resistance, and are the main components of sebum. It was found that the removal rate by wiping with water was 70% or more and the cleaning property was excellent.
On the other hand, from Comparative Example 1, the polycarbonate composition not containing sodium linear alkylbenzene sulfonate (B) and the side chain diamino polysiloxane compound (C1) has an oxygen index of 25 and a relatively low flame retardancy. The surface resistivity was 10 ¹⁷ Ω or more, and the removal rate of the oleic acid and artificial sebum, which are the main components of sebum, by wiping with water was 30 to 60%, indicating that the detergency was poor. From Comparative Example 2, a polycarbonate composition containing only sodium linear alkylbenzene sulfonate (B) has a surface resistivity of 10 ¹⁴ Ω or less, excellent dust resistance, and oleic acid or artificial sebum, which is the main component of sebum. It was found that although the removal rate by water wiping was 70% or more and excellent in cleanability, the oxygen index was 24 and inferior in flame retardancy. From Comparative Example 3, the polycarbonate composition containing 3% by mass of linear alkylbenzene sulfonate sodium (B) and 7% by mass of the side-chain diamino type polysiloxane compound (C1) has a relatively high flame retardant property with an oxygen index of 33. However, the surface resistivity is 10 ¹⁶ Ω or more and the dust resistance is poor. Further, it was found that oleic acid, which is the main component of sebum, and artificial sebum were removed with a water wipe of less than 60%, resulting in poor cleaning and bleeding.

From Comparative Example 4, the polycarbonate composition containing 3% by mass of linear alkylbenzene sodium sulfonate (B) and 3% by mass of the side chain monoamino polysiloxane compound (C2) has an oxygen index of 33 and a relatively high flame retardancy. However, it was found that the surface resistivity was 10 ¹⁶ Ω or more, which was inferior in dust resistance, and the removal rate of oleic acid or artificial sebum, which is the main component of sebum, by wiping with water was 40-60%, which was inferior in cleanability. From Comparative Examples 5 to 6, in the polycarbonate composition containing 3% by mass of linear alkylbenzene sulfonate sodium (B) and 3% by mass of epoxy group-containing polysiloxane compound (D), or 3% by mass of polysiloxane compound (E), It has a relatively low flame resistance with an oxygen index of 25, a surface resistivity of 10 ¹⁷ Ω or more, inferior dust resistance, and a removal rate of oleic acid or artificial sebum, which is the main component of sebum, by wiping with water. It was found that the cleaning performance was inferior to 50%.

From the results of Examples 4 to 6, polycarbonate (PC) was mixed with 1% to 5% by mass of linear alkylbenzene sulfonate (B) 3% by mass and side chain diamino polysiloxane compound (C1), and polytetrafluoroethylene. Polycarbonate composition containing 0.5% by mass of (F) has high flame retardancy with an oxygen index of 30 or more, and self-extinguishes with an average afterflame time of less than 10 seconds without dripping according to UL94V evaluation. Excellent flammability, 0, excellent impact strength, surface resistivity of 10 ¹⁵ Ω or less, excellent dust resistance, and removal of oleic acid and artificial sebum, the main component of sebum, by wiping with water It was found that the rate was 70% or more and the cleaning property was excellent. From the result of Comparative Example 7, the polycarbonate composition in which only 0.5% by mass of polytetrafluoroethylene (F) is blended with polycarbonate (PC) has a relatively low flame resistance of 25, and UL94V Although it did not drip in the evaluation, it did not satisfy V-2 because it did not self-extinguish. In addition, although it is excellent in impact strength, its surface resistivity is 10 ¹⁷ Ω or more and it is inferior in dustproofness, and its removal rate by wiping off oleic acid or artificial sebum, which is the main component of sebum, is 60% or less, and it is inferior in cleanability. I understood that. Also, from Comparative Example 8, 3% by mass of linear alkylbenzene sulfonate (B), 7% by mass of the side chain diamino type polysiloxane compound (C1), and 0.5% by mass of polytetrafluoroethylene (F) Although the polycarbonate composition is highly flame retardant with an oxygen index of 32 and UL94V of V-0, the surface resistivity is 10 ¹⁶ Ω or more and is inferior in dust resistance. Further, it was found that oleic acid, which is the main component of sebum, and artificial sebum were removed with a water wipe of less than 60%, resulting in poor cleaning and bleeding.

  Applied to various fields such as OA (office automation) equipment, information / communication equipment, electrical equipment, etc., vehicle field, construction field, etc., in particular, electronic equipment that can be operated by an unspecified number of people, for example, It is suitable for components such as ATM terminals, POS terminals, compound copying machines, servers, smartphone terminals, and tablet terminals.

Claims (5)

A polycarbonate resin, a polysiloxane compound represented by the formula (1) in a range of 0.1% by mass to 5% by mass with respect to the polycarbonate resin, and 0.01% by mass or more with respect to the polycarbonate resin. A polycarbonate-based resin composition having a number average molecular weight of 900 or more and 120,000 or less, wherein the polysiloxane compound represented by formula (1) is blended with a sulfonate represented by formula (2) in a range of 5% by mass or less. object.

@ 0007

(In the formula, R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are an alkyl group, alkenyl group, aryl group, aralkyl group, alkylaryl group, or — (CH ₂ ) _α- NH—C having 18 or less carbon atoms. ₆ H ₅ (α is an integer of 1 to 8), which may be the same or different from each other, may be wholly or partially substituted with a halogen atom, and R ₈ and R ₉ are divalent organic groups. M and p are numerical values of m ≧ 0 and p> 0, respectively.)
R ₁₀ -SO ₃ M ⁺ (2)
(Wherein R ₁₀ represents an alkyl group having 1 to 40 carbon atoms, an aralkyl group having 6 to 40 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and M ⁺ represents a metal ion or an organic onium ion.)   Furthermore, the polycarbonate-type resin composition of Claim 1 which mix | blended the fiber-forming type fluorine-containing polymer in 0.05 mass% or more and 1 mass% or less with respect to polycarbonate-type resin.   A molded product molded from the polycarbonate resin composition according to claim 1.   A process for producing a polycarbonate-based resin composition in which a polycarbonate-based resin in a molten state, a polysiloxane compound represented by formula (1), and a sulfonate represented by formula (2) are subjected to a shearing action and mixed and stirred. .   Furthermore, the manufacturing method of the polycarbonate-type resin composition of Claim 4 which mixes and stirs a fiber formation type fluorine-containing polymer.