JP6713272B2 - Polycarbonate-based resin composition, product, housing-forming resin, method of using polycarbonate-based resin composition as housing-forming resin, and method of manufacturing polycarbonate-based resin composition - Google Patents

Description

The present invention provides a polycarbonate-based resin composition having both antibacterial properties and flame retardancy, a product, a housing-forming resin, a method of using the polycarbonate-based resin composition as a housing-forming resin, and a polycarbonate-based resin composition. It relates to a manufacturing method.

Conventionally, aromatic polycarbonate resins have excellent mechanical properties, thermal properties, dimensional stability, etc., and are therefore resin molded products used as durable consumer products for electronic and electrical equipment, office automation equipment, information and communication equipment, etc. Is used in a wide range of applications.

In recent years, from the viewpoint of improving the safety of products, it has been required to make resin molded parts flame-retardant mainly for housings of products. As a method of imparting flame retardancy to a resin material, a method of kneading and adding a flame retardant such as a halogen compound or a phosphorus compound is generally used. However, in recent years, it has been reported that organic compounds containing halogen adversely affect the environment and the human body, and non-halogenated flame retardants are becoming popular mainly in Europe. Flame retardant technology is being developed.

On the other hand, due to increasing cleanliness in society, products with antibacterial properties added to parts that may be touched by people have become popular, and in order to improve the added value of products, it is necessary to add antibacterial properties to resin molded parts. It has been demanded. As a method of imparting antibacterial properties to resin molded parts, a method of kneading and adding an antibacterial agent to a resin material is generally used, as in the case of the above flame retardant, and a method of coating the surface of the resin molded part with the antibacterial agent. Is also used. However, although the method of coating the antibacterial agent shows sufficient antibacterial performance at the initial stage, it can be said that the method of kneading and adding the antibacterial agent is excellent because of its low long-term sustainability. Examples of the antibacterial agent include organic compounds and inorganic compounds. Inorganic compounds are generally used from the viewpoint of durability, heat resistance, and particularly safety.

Under such social needs, in order to obtain a resin material having both antibacterial and flame retardant properties, it is necessary to add both an antibacterial agent and a flame retardant to the resin as a raw material.

However, when an inorganic antibacterial agent is added to an aromatic polycarbonate-based resin containing a phosphorus-based flame retardant, the antibacterial property is higher than that of an aromatic polycarbonate-based resin not containing a phosphorus-based flame retardant added with an inorganic antibacterial agent. There was a problem that it was difficult to develop.

Furthermore, when an inorganic antibacterial agent is added to an aromatic polycarbonate resin containing a phosphorus flame retardant, there is a problem that flame retardancy is reduced as compared with a system in which an inorganic antibacterial agent is not added. In addition, if a large amount of inorganic antibacterial agent is added, sufficient antibacterial property is exhibited, but there is a problem that mechanical properties and thermal properties are greatly deteriorated along with the decrease in flame retardancy described above. Is difficult to use.

In order to solve these problems, JP 2001-115040 A (Patent Document 1) proposes a resin composition in which a thermoplastic resin such as polycarbonate is blended with an organic cyclic phosphorus compound having both flame retardancy and antibacterial properties. There is.

Further, in JP-A-11-5910 (Patent Document 2), zinc carbonate and a flame retardant are added to a thermoplastic resin, and the thermal decomposition of zinc carbonate during melt kneading is utilized to make the resin composition flame retardant. A method of imparting antibacterial properties has been proposed.

JP 2001-115040 A JP, 11-5910, A

However, it is difficult for the methods described in Patent Document 1 and Patent Document 2 to have both antibacterial properties and flame retardancy. From the above, an object of the present invention is to provide a polycarbonate resin composition having both antibacterial properties and flame retardancy.

According to an embodiment of the present invention, an aromatic polycarbonate resin (A) containing a phosphorus flame retardant, a zirconium phosphate (B) containing a silver antibacterial component, and a polyether ester amide (C) are included. , A polycarbonate resin composition having an antibacterial activity value of 2.0 or more as defined in JIS Z2801 and a flammability classification of UL94 standard of V-1 or V-0 is provided.

Preferably, 0.5 parts by weight or more and 3 parts by weight or less of zirconium phosphate (B) containing the silver-based antibacterial component is included with respect to 100 parts by weight of the aromatic polycarbonate-based resin (A) containing the phosphorus-based flame retardant. , 0.05 parts by weight or more and 0.5 parts by weight or less of the polyether ester amide (C).

Preferably, the phosphorus flame retardant is an aromatic condensed phosphoric acid ester.

Preferably, the aromatic polycarbonate-based resin includes a polymer alloy or a polymer blend of an aromatic polycarbonate resin and an acrylonitrile-butadiene-styrene copolymer. The polymer alloy or polymer blend contains at least 50% by weight of the aromatic polycarbonate resin.

According to another aspect of the present invention, 0.5 part by weight or more of zirconium phosphate (B) containing a silver-based antibacterial component is added to 100 parts by weight of an aromatic polycarbonate-based resin (A) containing a phosphorus-based flame retardant. Provided is a polycarbonate-based resin composition containing not more than parts by weight and not less than 0.05 parts by weight and not more than 0.5 parts by weight of a polyether ester amide (C).

According to another aspect of the present invention, there is provided a product having a housing containing the above polycarbonate-based resin composition.

According to another aspect of the present invention, a housing-forming resin containing the above polycarbonate-based resin composition as a main component is provided.

According to another aspect of the present invention, there is provided a method of using the above polycarbonate-based resin composition as a housing-forming resin.

According to another aspect of the present invention, a mixture of zirconium phosphate (B) containing a silver antibacterial component and polyetheresteramide (C) is added to an aromatic polycarbonate resin (A) containing a phosphorus flame retardant. Provided is a method for producing a polycarbonate-based resin composition, which comprises a step of blending and a step of heating, melting, and kneading the mixture and the aromatic polycarbonate-based resin (A) containing the phosphorus-based flame retardant.

As described above, the present invention provides a polycarbonate resin composition having both antibacterial properties and flame retardancy.

<First Embodiment>
Hereinafter, the polycarbonate resin composition having antibacterial properties and flame retardancy according to the present embodiment will be described in detail.

The polycarbonate resin composition having antibacterial properties and flame retardancy according to the present embodiment is an aromatic polycarbonate resin (A) containing at least a phosphorus flame retardant, and a zirconium phosphate containing a silver antibacterial component (B). ), and polyether ester amide (C).
<Aromatic Polycarbonate Resin (A) Containing Phosphorus Flame Retardant>

As the aromatic polycarbonate resin, an aromatic polycarbonate resin (hereinafter, also referred to as a PC resin), a mixture of an aromatic polycarbonate resin and another thermoplastic resin (polymer alloy or polymer blend), etc. are preferably used. .. Examples of the thermoplastic resin include acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES), acrylonitrile-styrene-acrylate copolymer (ASA), acrylonitrile- Ethylene-propylene-diene-styrene copolymer (AEPDMS), acrylonitrile-styrene copolymer (AS), polystyrene (PS), styrene-butadiene copolymer (HIPS), polymethylmethacrylate (PMMA), polyphenylene oxide (PPO). ), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyamide (PA), and the like, and any one or a plurality of these may be mixed and used. Among these polymer alloys or polymer blends, a polymer alloy or polymer blend of aromatic polycarbonate resin and acrylonitrile-butadiene-styrene copolymer (hereinafter, also referred to as PC/ABS resin) is particularly preferably used.

As such a PC resin, a resin produced by reacting a carbonate precursor with a dihydric phenol can be used. Examples of the reaction method include an interfacial polymerization method, a transesterification method, and a ring-opening polymerization method. The carbonate precursor and the dihydric phenol are not particularly limited and various ones can be used. Among these, those synthesized by interfacial polycondensation of bisphenol A and carbonyl dichloride or transesterification polymerization of bisphenol A and diphenyl carbonate are more preferable.

Further, as the PC resin contained in the above PC/ABS resin, a resin produced by reacting a carbonate precursor with a dihydric phenol can be used. Examples of the reaction method include an interfacial polymerization method, a transesterification method, and a ring-opening polymerization method. The carbonate precursor and the dihydric phenol are not particularly limited and various ones can be used. Among these, those synthesized by interfacial polycondensation of bisphenol A and carbonyl dichloride or transesterification polymerization of bisphenol A and diphenyl carbonate are more preferable.

Further, the ABS resin contained in the above PC/ABS resin is preferably an ABS resin synthesized by bulk polymerization. Since ABS resin synthesized by bulk polymerization does not contain impurities such as emulsifiers, hydrolysis of PC resin due to impurities is suppressed, and a machine of a polycarbonate resin composition having antibacterial properties and flame retardancy according to the present embodiment. Strength and flame retardancy are improved.

Further, the PC/ABS resin preferably contains at least 50% by weight of PC resin. By setting the content ratio of the PC resin to be 50% by weight or more, the rigidity and flame retardancy of the final objective polycarbonate resin composition having antibacterial properties and flame retardancy can be improved. Further, from the viewpoint of the balance between rigidity and flame retardancy, it is more preferable that the PC/ABS resin contains 60% by weight or more and 80% by weight or less of the PC resin.

The weight average molecular weight of the aromatic polycarbonate resin (A) according to the present embodiment is not particularly limited as long as it is within a range where it can be normally molded and processed, but it is 40,000 or more and 60,000 or less. The range of is preferable. By setting the weight average molecular weight of the aromatic polycarbonate resin (A) to 60,000 or less, the processability of the polycarbonate resin composition having antibacterial properties and flame retardancy of the final object becomes good, and the above-mentioned weight is increased. By setting the average molecular weight to 40,000 or more, mechanical strength such as impact strength can be improved.

The weight average molecular weight here is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC). Further, the above-mentioned weight average molecular weight includes an error of about 10% because the measured values vary depending on the GPC measurement conditions and measurement environment.

なお、上記の式（１）中、Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄は、水素原子又は有機基を示し、Ｒ₅は２価以上の有機基を示し、ｉは０又は１であり、ｊは１以上の整数であり、ｋは０以上の整数を示す。 Further, a phosphorus-based flame retardant is used as the flame retardant contained in the aromatic polycarbonate-based resin according to the present invention, a condensed phosphoric acid ester represented by the following general formula (1) is preferable, and an aromatic condensed phosphoric ester is Particularly preferred.

In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or an organic group, R ₅ represents a divalent or higher valent organic group, and i is 0 or 1. , J is an integer of 1 or more, and k is an integer of 0 or more.

The organic group is an alkyl group including a substituted one, a cycloalkyl group, an aryl group or the like. When it is substituted, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an arylthio group. Further, an arylalkoxyalkyl group or the like which is a group in which these substituents are combined, or an arylsulfonylaryl group or the like in which these substituents are bonded by an oxygen atom, a nitrogen atom, a sulfur atom or the like is used as a substituent. Etc.

Further, the divalent or higher valent organic group R ₅ means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to carbon atoms from the above-mentioned organic group. For example, it is derived from an alkylene group, a (substituted)phenylene group, or a bisphenol which is a polynuclear phenol. Preferred are bisphenol A, resorcinol, dihydroxydiphenyl and the like.

The phosphate ester compound may be a monomer, a dimer, an oligomer, a polymer or a mixture thereof. Specifically, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tris(2-ethylhexyl) phosphate, diisopropyl. Phenyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, bisphenol A bisphosphate, resorcin bisphosphate, resorcinol-diphenyl phosphate, trioxybenzene triphosphate, cresyl diphenyl phosphate, or their substitution products, condensates, etc. Can be mentioned. Of these, 1,3-phenylene bisdixylenyl phosphate, which is solid at room temperature and easy to handle, has high water resistance and high char-forming ability, is particularly preferable.

The phosphorus-based flame retardant is preferably blended in an amount of 0.1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the aromatic polycarbonate resin. The aromatic polycarbonate-based resin according to the present embodiment preferably contains only a phosphorus-based flame retardant, and preferably does not contain a halogen-based flame retardant.

Further, for the purpose of improving the flame retardancy of the polycarbonate resin composition having antibacterial properties and flame retardancy according to the present embodiment, a flame retardant aid may be blended, if necessary. As the flame retardant aid, any fluorine-containing polymer can be used without particular limitation as long as it is capable of forming fibrils. Specific examples thereof include polydifluoroethylene, polytetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylene copolymer, and a tetrafluoroethylene-olefin (ethylene, propylene, etc.)-based monomer copolymer. Among them, polytetrafluoroethylene is preferable. These can be used alone or in combination. Polytetrafluoroethylene having a fibril-forming ability has an extremely high molecular weight, and tends to bind to each other by an external action such as a shearing force to form a fibrous form. The molecular weight is 1,000,000 or more and 10,000,000 or less, more preferably 2,000,000 or more and 9,000,000 or less in the number average molecular weight obtained from the standard specific gravity.

The number average molecular weight as referred to herein is a polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC). Further, the above-mentioned weight average molecular weight includes an error of about 10% because the measured values vary depending on the GPC measurement conditions and measurement environment.

Polytetrafluoroethylene capable of forming fibrils can be used in the form of solid or aqueous dispersion. Further, polytetrafluoroethylene having such fibril-forming ability improves dispersibility in a resin, and in order to obtain better flame retardancy and mechanical properties, a polytetrafluoroethylene mixture in a mixed form with another resin is used. It is also possible to use. In order to improve the compatibility with the aromatic polycarbonate resin (A) containing a phosphorus flame retardant, it is particularly preferable to use acrylic-modified polytetrafluoroethylene.

The above-mentioned fluorinated polymer capable of forming fibrils is preferably blended in an amount of 0.1 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the aromatic polycarbonate resin.

In this embodiment, a newly manufactured virgin material is used as the aromatic polycarbonate resin (A). However, as the aromatic polycarbonate resin (A), waste materials generated in the manufacturing process of other products or the same products, or waste materials recovered from the discarded products, such as flat-screen TVs, air conditioners, refrigerators, washing machines, and microwave ovens. , Collected materials such as personal computers and printers, and waste materials may be used.
<Zirconium phosphate (B) containing a silver-based antibacterial component>

Zirconium phosphate (B) containing a silver-based antibacterial component is added for the purpose of imparting antibacterial properties to the resin composition according to the present embodiment. It is a compound carrying an antibacterial component.

As zirconium phosphate, hexagonal zirconium phosphate is preferable.

The silver-based antibacterial component is not particularly limited, and known ones such as silver, silver complex, and silver compound can be used.

Further, in the zirconium phosphate (B) containing a silver-based antibacterial component, the content of the silver-based antibacterial component contained in the zirconium phosphate is not particularly limited, but the cost-effective antibacterial property-providing effect is obtained. It is preferable that the maximum range is 0.1% by weight or more and 5% by weight or less.

Further, the primary particle diameter of zirconium phosphate (B) containing a silver-based antibacterial component is preferably 5 μm or less. By setting the primary particle diameter of zirconium phosphate (B) containing a silver-based antibacterial component to 5 μm or less, the flame retardancy and impact strength of the polycarbonate resin composition having antibacterial properties and flame retardancy of the final object can be improved. It will be good.

The addition amount of zirconium phosphate (B) containing a silver antibacterial component is 0.5 parts by weight or more and 3 parts by weight or less with respect to 100 parts by weight of the aromatic polycarbonate resin (A) containing a phosphorus flame retardant, It is preferable to mix it, and it is more preferable to add 1 part by weight or more and 2 parts by weight or less. The antibacterial property of the polycarbonate resin composition having antibacterial properties and flame retardancy according to the present embodiment is adjusted by adding 0.5 part by weight or more of zirconium phosphate (B) containing a silver antibacterial component. Will be good. When the amount is 3 parts by weight or less, the flame retardancy and impact strength of the polycarbonate resin composition having antibacterial properties and flame retardancy according to the present embodiment are improved.
<Polyether ester amide (C)>

In order to exhibit the antibacterial property in the resin molded product, it is preferable that the antibacterial agent is present near the surface of the resin molded product (exposed on the surface). When the polyether ester amide (C) and zirconium phosphate (B) containing a silver-based antibacterial component are added together, the antibacterial performance is higher than that of a system containing only zirconium phosphate (B) containing a silver-based antibacterial component. Will be good.

In a resin molded product in which the polyether ester amide (C) and the aromatic polycarbonate resin (A) containing a phosphorus flame retardant are blended, the polyether ester amide (C) has a characteristic that it tends to collect near the surface of the resin molded product. In addition, the polyether ester amide (C) has a characteristic that it has a high affinity with zirconium phosphate (B) containing a silver-based antibacterial component.

Therefore, when the polyether ester amide (C) and the zirconium phosphate (B) containing the silver-based antibacterial component are added together, the polyether ester amide (C) contains zirconium phosphate (B) containing the silver-based antibacterial component. Since the surface exposure property of B) is improved, the effect of adding the antibacterial agent is enhanced. That is, even if it is added in a small amount, sufficient antibacterial properties are exhibited, so that the reduction in flame retardancy can be suppressed.

The polyether ester amide (C) is a block copolymer obtained by ester-linking a polyamide component having carboxyl groups at both ends and a polyether component which is a polymer obtained by ether-linking bisphenols and the like. There is no particular limitation as long as it has a structural unit represented by the following general formula (2).
_{- (O- (CH 2 -CH 2} -O) x - (CO- (CH 2) y -NH) z -CO-R-CO) n -
...General formula (2)
In the above formula (2), x, y, z and n represent the number of repetitions and R represents an alkyl group.

The polyether ester amide (C) is preferably added in an amount of 0.05 parts by weight or more and 0.5 parts by weight or less based on 100 parts by weight of the aromatic polycarbonate resin (A) containing a phosphorus flame retardant. It is more preferable to add 0.1 part by weight or more and 0.2 part by weight or less. By setting the addition amount of the polyether ester amide (C) to 0.05 parts by weight or more, the antibacterial property of the polycarbonate resin composition having antibacterial property and flame retardancy becomes good. Further, when the amount of the polyether ester amide (C) added is 0.5 parts by weight or less, the flame retardancy of the polycarbonate resin composition having antibacterial properties and flame retardancy becomes good.

In addition to the above-mentioned components, the resin composition according to the present embodiment may optionally include conventionally known additives within a range that does not impair the effects according to the present embodiment. In this case, as additives, antioxidants (phenolic, phosphorus, sulfur, etc.), ultraviolet absorbers (benzophenone, hindered amine, etc.), impact modifiers (acrylic rubber, diene rubber, etc.), Anti-hydrolysis agent (carbodiimide compound, etc.), anti-drip agent (fluorine resin), filler (glass fiber, mica, talc, calcium carbonate, barium sulfate, etc.), lubricant, plasticizer, stabilizer, release agent, charging Examples include one or more of inhibitors, colorants (pigments, dyes, etc.), metal deactivators, neutralizing agents, dispersants, and the like.

The polycarbonate resin composition having antibacterial properties and flame retardancy according to the present embodiment includes, for example, an aromatic polycarbonate resin (A) containing a phosphorus flame retardant and a zirconium phosphate (A) containing a silver antibacterial component. It can be manufactured by a method in which B) and the polyether ester amide (C) are simultaneously blended, uniformly mixed, and heated and melted.

However, in the polycarbonate resin composition, zirconium phosphate (B) containing a silver antibacterial component and polyetheresteramide (C) are uniformly mixed in advance, and then zirconium phosphate (B) containing a silver antibacterial component is prepared. It is more preferable that the mixture of the compound (1) and the polyether ester amide (C) is blended with the aromatic polycarbonate resin (A) containing a phosphorus flame retardant, and the mixture is heated and melted to produce. According to this method, the affinity between the zirconium phosphate (B) containing the silver antibacterial component and the polyether ester amide (C) in the aromatic polycarbonate resin (A) containing the phosphorus flame retardant is further increased. Therefore, the effect of adding zirconium phosphate (B) containing a silver-based antibacterial component becomes higher.

In the present embodiment, the polyether ester amide (C) containing zirconium phosphate (B) containing the silver antibacterial component and the aromatic polycarbonate resin (A) containing the phosphorus flame retardant are It is a phase separation system.

A known method can be used in the method for producing the resin composition according to the present embodiment. In the resin composition according to the present embodiment, for uniform mixing, melt kneading, and molding, for example, a blender, a Banbury mixer, a heating roll, a single-screw extruder, a multi-screw extruder or the like can be preferably used. ..

Further, to give an example of injection molding conditions suitable for the resin composition according to the present embodiment, the cylinder temperature is set to the melting point or the flow start temperature of the resin composition or higher, for example, 220° C. or higher and 280° C. or lower, preferable.

When the resin composition according to the present embodiment is molded into pellets, methods such as sheet cutting, strand cutting, hot air cutting, and underwater cutting can be preferably used. Among these methods, in the case where the thermoplastic resin composition can be smoothly supplied when it is molded into a specific shape by injection molding later, underwater cutting is particularly preferable because it can be used for large-scale processing.
<Example>

Hereinafter, the polycarbonate resin composition having antibacterial and flame retardant properties according to the present embodiment will be described with reference to specific examples, but naturally the present invention is not limited to the following examples. ..

First, the components (A) to (C) used in Examples and Comparative Examples will be described.
(A) Component A-1: Polymer alloy of aromatic PC resin and ABS resin containing phosphate ester flame retardant A-2: Polymer alloy waste material of aromatic PC resin and ABS resin recovered from a used LCD TV (B) ) Component B-1: Zirconium phosphate-supporting silver-based antibacterial agent (Novalon AGZ330: Toa Gosei)
Other than component (B) B'-1: Zeolite-supported silver-based antibacterial agent (Bactequila BM102GA: Fuji Chemical)
(C) Component C-1: Polyether ester amide compound (Perestat NC6321: Sanyo Chemical Industries)
Other than component (C) C'-1: Magnesium stearate (Dahachi Chemical Industry)
(Other)
・Phosphorus flame retardant: Aromatic condensed phosphoric acid ester (PX200: Daihachi Chemical Industry)
・Anti-drip agent: Modified polytetrafluoroethylene (Metabrene A3750: Mitsubishi Rayon)
・Impact modifier: Glycidyl methacrylate resin/silicone resin core/shell rubber (Metabrene S-2200: Mitsubishi Rayon)
<Examples and Comparative Examples>

The components shown above were blended at the blending ratios shown in Tables 1 to 6 and uniformly mixed using a tumbler mixer, and then a biaxial melt kneading with a screw diameter of 25 mm and an effective screw length L/D=26. Using an extruder (manufactured by Technovel), the mixture was heated and melted and kneaded at a set temperature of 250 degrees, extruded into a strand shape, and cut using a pelletizer to obtain a pellet-shaped resin composition. The extrusion conditions were a discharge rate of 12 kg/h, a screw rotation speed of 150 rpm, and a feeder rotation speed of 50 rpm. The pelletized resin composition was dried using a hot air dehumidifying dryer (Matsui Seisakusho) at 80° C. for 6 hours, and then a 10 ton vertical injection molding machine (Nissei Plastic Industry Co., Ltd.) or 80 Ton horizontal injection molding machine (manufactured by NISSEI PLASTIC INDUSTRIAL CO., LTD.) under the injection molding conditions of set temperature of 260°C, mold temperature of 60°C, and cooling time of 30 seconds. Test pieces and ASTM-compliant test pieces for measuring physical properties were prepared.
(Evaluation method)

The following evaluation was performed using each test piece produced as Examples 1-15 and Comparative Examples 1-2.
(1) Antibacterial property A 50 mm×50 mm×2.5 mm flat plate molded product was prepared and subjected to an antibacterial test with Escherichia coli and Staphylococcus aureus according to JIS Z2801:2010. The evaluation of antibacterial property was determined by the antibacterial activity value defined in JIS Z2801. When the antibacterial activity value is 2.0 or more, it can be said to have an antibacterial effect.
(2) Flame retardance A vertical combustion test piece having a length of 127 mm, a width of 13 mm, and a thickness of 1.5 mm was prepared according to the UL94 standard, and a vertical combustion test was performed according to the UL94 standard to determine the combustibility category. In addition, when all the criteria of V-0, V-1, and V-2 are not satisfied, it is determined to be V-2 or less.
(3) Izod impact strength A test piece for physical property measurement conforming to ASTM was prepared, and the notched Izod impact strength was measured according to JIS K7110.
(4) Flexural Modulus A test piece for measuring physical properties conforming to ASTM was prepared and the flexural modulus was measured according to JIS K7171.

Hereinafter, the evaluation results of Examples 1 to 9 and Comparative Examples 1 to 8 will be described in detail. As a performance standard of the polycarbonate resin composition, it is preferable that the antibacterial activity value is 2.0 or more and the vertical flammability category is V-1 or more. In particular, regarding the polycarbonate-based resin composition used for the case of durable consumer products, in addition to the above conditions, at least one of Izod impact strength of 6.0 kJ/m2 or more and bending elastic modulus of 2200 MPa or more must be satisfied. Is preferred.

First, referring to Table 1, in Example 1 and Comparative Example 1, by combining a polyether ester amide compound (C-1) with a zirconium phosphate-supporting silver-based antibacterial agent (B-1), phosphoric acid It can be seen that the dispersibility of the zirconium-supported silver antibacterial agent (B-1) is improved and sufficient antibacterial properties are obtained. Furthermore, since the dispersibility of the zirconium phosphate-supporting silver-based antibacterial agent (B-1) is improved, it is possible to suppress a decrease in flame retardancy.

On the other hand, in Comparative Example 2, when the polyether ester amide compound (C-1) was not added, a large amount of zirconium phosphate-supported silver antibacterial agent (B-1) was added in order to obtain sufficient antibacterial property. Need to be added. However, it is understood that when a large amount of zirconium phosphate-supporting silver-based antibacterial agent (B-1) is added, the flame retardancy and impact strength are greatly reduced among the examples, as compared with, for example, the example 1.

Next, referring to Table 2, regarding Examples 2 to 5 and Comparative Examples 3 and 4, in particular, in order to satisfy antibacterial properties, flame retardancy, and mechanical properties, an aroma containing a phosphate ester flame retardant. The addition amount of the zirconium phosphate-supporting silver-based antibacterial agent (B-1) to 100 parts by weight of the polymer alloy (A-1) of the group PC resin and the ABS resin is preferably 0.5 to 3 parts by weight. It can be seen that it is more preferable to be 2 parts by weight.

Next, referring to Table 3, regarding Examples 3, 6 to 8 and Comparative Examples 5 and 6, in particular, in order to satisfy the antibacterial property, the flame retardancy, and the mechanical properties, a phosphoric acid ester-based flame retardant was used. The addition amount of the polyether ester amide compound (C-1) to 100 parts by weight of the polymer blend or polymer alloy (A-1) of the aromatic PC resin and the ABS resin containing is 0.05 to 0.5 parts by weight. It is found that the amount is preferably 0.1 to 0.2 part by weight, and more preferably 0.1 to 0.2 part by weight.

Further, with reference to Table 4, in the case of adding zirconium phosphate-supporting silver-based antibacterial agent (B-1) in Example 3 and Comparative Example 7, zeolite-supported which is a general silver-based antibacterial agent. It can be seen that the antibacterial property, flame retardancy, and impact strength are improved as compared with the case where the silver-based antibacterial agent (B'-1) is added.

Further, referring to Table 5, regarding Example 3 and Comparative Example 8, magnesium stearate (C′−), which is a general dispersant, was added when the polyetheresteramide compound (C-1) was added. It can be seen that the antibacterial property, flame retardancy and impact strength are improved as compared with the case of adding 1).

Further, referring to Table 6, regarding Examples 3 and 9, as an aromatic polycarbonate resin (A) containing a phosphorus flame retardant, a polymer alloy waste material of an aromatic PC resin and an ABS resin recovered from a used liquid crystal television. Even if (A-2) is utilized, an antibacterial property equivalent to that of a resin composition using a polymer alloy (A-1) of an aromatic PC resin containing a phosphate ester flame retardant that is a virgin material and an ABS resin, It can be seen that flame retardancy and mechanical strength can be obtained.

From the above, at least the aromatic polycarbonate-based resin (A), the zirconium phosphate (B) containing the silver-based antibacterial component, and the polyether ester amide (C) are blended in a predetermined ratio to produce an electron -As a resin molded part used in the case of durable consumer materials such as electrical equipment, office automation equipment, information and communication equipment, etc., it has mechanical properties that can be used in a wide range of applications, and has high antibacterial properties and flame retardancy. It is possible to obtain a polycarbonate resin composition having both of the following and a product containing them.

The casing-forming resin preferably contains the polycarbonate-based resin composition as a main component, and preferably contains, for example, 50% by weight or more of the polycarbonate-based resin composition, and 70% by weight of the polycarbonate-based resin composition. It is more preferable that the content of the polycarbonate-based resin composition is 90% by weight or more.

More specifically, with the method described in Patent Document 1, it is difficult to obtain sufficient flame retardancy, and the flame retardancy required for durable consumer goods has not been satisfied. In addition, according to the method described in Patent Document 2, when zinc carbonate is added to a resin having hydrolyzability such as polycarbonate or polyester, the resin composition obtained by the heat at the time of melt-kneading and the water generated at the time of thermal decomposition is There is a fear that the flame retardancy, mechanical properties, and thermal properties will be greatly reduced due to the progress of lower molecular weight. In that respect, the polycarbonate resin composition according to the present embodiment can have flame retardancy and antibacterial properties without deteriorating mechanical properties and thermal properties.
<Second Embodiment>

In the first embodiment, the polycarbonate resin composition is used for electronic/electrical devices, OA devices, information/communication devices, and the like. However, in this embodiment, the aromatic polycarbonate resin (A), the zirconium phosphate (B) containing the silver antibacterial component, and the polyether ester amide (C) are mixed in a predetermined ratio. The polycarbonate resin composition may be used not only in electric devices but also in other types of products such as cooking utensils and toys.

The embodiments disclosed this time are to be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the above description but by the claims, and is intended to include meanings equivalent to the claims and all modifications within the scope. For example, various modifications are possible within the scope of the claims, and embodiments obtained by appropriately combining the respective technical means disclosed as different embodiments are also included in the technical scope of the present invention. ..

Claims (9)

An aromatic polycarbonate resin (A) containing a phosphorus flame retardant in which 0.1 to 30 parts by weight of a phosphorus flame retardant is mixed with 100 parts by weight of an aromatic polycarbonate resin, and a silver antibacterial component. Containing zirconium phosphate (B) and polyether ester amide (C) contained,
The aromatic polycarbonate-based resin (A) includes an aromatic polycarbonate resin or a polymer alloy or polymer blend of an aromatic polycarbonate resin and another thermoplastic resin, and the polymer alloy or polymer blend is the aromatic aromatic resin. Containing at least 50% by weight of a polycarbonate resin,
A polycarbonate-based resin composition having an antibacterial activity value of 2.0 or more specified in JIS Z2801, and a flammability classification of UL94 standard of V-1 or V-0. 0.5 parts by weight or more and 3 parts by weight or less of zirconium phosphate (B) containing the silver-based antibacterial component is added to 100 parts by weight of the aromatic polycarbonate-based resin (A) containing the phosphorus-based flame retardant, The polycarbonate-based resin composition according to claim 1, comprising 0.05 to 0.5 parts by weight of the ether ester amide (C). The polycarbonate resin composition according to claim 1 or 2, wherein the phosphorus flame retardant is an aromatic condensed phosphoric acid ester. The aromatic polycarbonate resin includes a polymer alloy or a blend of an aromatic polycarbonate resin and acrylonitrile-butadiene-styrene copolymer,
The polycarbonate resin composition according to any one of claims 1 to 3, wherein the polymer alloy or polymer blend contains at least 50% by weight of the aromatic polycarbonate resin. Silver based on 100 parts by weight of the aromatic polycarbonate-based resin (A) containing the phosphorus-based flame retardant in which 0.1 to 30 parts by weight of the phosphorus-based flame retardant is mixed with 100 parts by weight of the aromatic polycarbonate-based resin. system antimicrobial comprising component 3 parts by weight or less than 0.5 part by weight of zirconium phosphate (B) containing polyether ester amide (C) seen containing 0.5 parts by weight 0.05 parts by weight or more,
The aromatic polycarbonate-based resin (A) includes an aromatic polycarbonate resin or a polymer alloy or polymer blend of an aromatic polycarbonate resin and another thermoplastic resin, and the polymer alloy or polymer blend is the aromatic aromatic resin. A polycarbonate resin composition containing at least 50% by weight of a polycarbonate resin. A product having a housing containing the polycarbonate-based resin composition according to any one of claims 1 to 5. A housing-forming resin containing the polycarbonate-based resin composition according to any one of claims 1 to 5 as a main component. A method of using the polycarbonate resin composition according to any one of claims 1 to 5 as a resin for forming a casing. A mixture of zirconium phosphate (B) containing a silver-based antibacterial component and polyether ester amide (C) is used in which the phosphorus-based flame retardant is 0.1 part by weight or more and 30 parts by weight or more, based on 100 parts by weight of the aromatic polycarbonate-based resin. In the aromatic polycarbonate resin (A) containing a phosphorus-based flame retardant compounded in an amount of 1 part or less, 0.5 parts by weight or more and 3 parts by weight or less of (B) is added to 100 parts by weight of (A). A step of compounding so as to contain 0.05 part by weight or more and 0.5 part by weight or less,
Heating and melting and kneading the mixture and the aromatic polycarbonate-based resin (A) containing the phosphorus-based flame retardant ,
The aromatic polycarbonate resin (A) includes an aromatic polycarbonate resin or a polymer alloy or polymer blend of an aromatic polycarbonate resin and another thermoplastic resin, and the polymer alloy or polymer blend is the aromatic aromatic resin. Ru der those containing polycarbonate resin least 50 wt%, the production method of the polycarbonate resin composition.