JP2022092557A - Antibacterial polycarbonate resin composition and molded article - Google Patents

Abstract

To provide an antibacterial polycarbonate resin composition having all of high transparency, high antibacterial properties and high shock resistance, and heat resistance, wet heat resistance and chemical resistance.SOLUTION: An antibacterial polycarbonate resin composition contains, based on 100 pts.mass of an aromatic polycarbonate resin (A) having a viscosity average molecular weight of 17,000-28,000, 5-80 pts.mass of a thermoplastic resin (B) excluding the aromatic polycarbonate resin (A), having a tension elastic modulus according to ISO527-1.2 of 1.0-2.5 GPa and an elastic modulus according to ISO489 of 1.45-1.59, and 0.1-2.5 pts.mass of an inorganic oxide (C) containing at least one of Ag, Zn, Zr and Cu elements, and has a haze value in a plate of a thickness of 2 mm of 20% or less.SELECTED DRAWING: None

Description

The present invention relates to an antibacterial polycarbonate resin composition and a molded product, and more particularly to an antibacterial polycarbonate resin composition and a molded product having excellent high transparency and impact resistance.

Polycarbonate resin is a resin with high light transmittance and excellent transparency, and is widely used in electrical products, automobile parts, stationery, furniture, daily necessities, etc. because of its excellent heat resistance, moldability, and practical strength. ..

In recent years, due to the growing idea of hygiene and cleanliness, products with antibacterial properties have been favored for various resin molded products, and the recent coronavirus damage has given antibacterial properties to the resin materials used. It has become particularly strongly requested.

There are many products in which antibacterial properties are imparted to a polycarbonate resin, but there is a problem that the addition of an antibacterial agent reduces the transparency, which is one of the significant properties of the polycarbonate resin. Therefore, various antibacterial polycarbonate resin compositions have been proposed, which impart antibacterial properties and suppress the decrease in transparency. For example, Patent Document 1 proposes that a polycarbonate resin composition containing a glass having a specific composition for eluting silver ions and an antioxidant is excellent in antibacterial properties without causing a change in hue or poor transparency. Has been made.

However, the inorganic antibacterial agent has a drawback that the original transparency of the polycarbonate resin is significantly lowered when blended with the polycarbonate resin, and the transparency of the polycarbonate resin composition of the invention described in Patent Document 1 is insufficient. Also, there is a problem that the impact resistance is poor.

Japanese Patent No. 5388326

An object of the present invention is to solve the above-mentioned conventional problems and to provide an antibacterial polycarbonate resin composition having excellent impact resistance without deteriorating transparency (problem).

As a result of diligent studies to solve the above problems, the present inventors have made an aromatic polycarbonate resin having a specific viscosity average molecular weight, and a thermoplastic resin having a specific tensile elastic modulus and a specific refractive modulus. And, by containing an inorganic oxide containing a specific element in a specific amount in combination, it has high transparency, high impact resistance and high antibacterial property, and further has heat resistance, moisture heat resistance and chemical resistance. The present invention has been completed by finding that an antibacterial polycarbonate resin composition having all of the above can be obtained.
The present invention relates to the following antibacterial polycarbonate resin compositions and molded articles.

1. 1. With respect to 100 parts by mass of the aromatic polycarbonate resin (A) having a viscosity average molecular weight of 17,000 to 28,000, the tensile elasticity according to ISO527-1.2 is 1.0 to 2.5 GPa and the refractive index according to ISO489 is 1.45 to Inorganic oxide (C) containing 5 to 80 parts by mass of a thermoplastic resin (B) other than the aromatic polycarbonate resin (A), which is 1.59, and at least one Ag, Zn, Zr, or Cu element. An antibacterial polycarbonate resin composition containing 0.1 to 2.5 parts by mass and having a haze value of 20% or less on a plate having a thickness of 2 mm.
2. 2. The polycarbonate resin composition according to 1 above, further containing 0.01 to 0.15 parts by mass of the phosphorus-based stabilizer (D) with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
3. 3. The polycarbonate resin composition according to 1 or 2 above, wherein the thermoplastic resin (B) is an amorphous thermoplastic polyester resin.
4. The thermoplastic resin (B) is a thermoplastic polyester resin containing a terephthalic acid residue, a 1,4-cyclohexanedimethanol residue, and a 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue. The polycarbonate resin composition according to any one of 1 to 3 above.
5. The thermoplastic resin (B) is a carboxylic acid unit in which the carboxylic acid constituent unit is selected from at least one of a terephthalic acid residue, an isophthalic acid residue, and a 1,4-cyclohexanedicarboxylic acid residue, and is derived from a diol. The constituent unit is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane in an amount of 10 to 100 mol% of all diol constituent units. , And the polycarbonate resin composition according to any one of 1 to 3 above, which is a thermoplastic polyester resin containing ethylene glycol or 1,4-cyclohexanedimethanol in an amount of 90 to 0 mol% in the total diol constituent unit.

6. The polycarbonate resin composition according to any one of 1 to 5 above, wherein the inorganic oxide (C) has a refractive index of 1.45 to 1.59 according to ISO489.
7. The polycarbonate resin composition according to any one of 1 to 6 above, wherein the inorganic oxide (C) is an inorganic oxide having an elution ability of Ag, Zn, Zr or Cu ions.
8. The polycarbonate resin composition according to 2 above, wherein the phosphorus-based stabilizer (D) is a stearyl acid phosphate-based stabilizer.
9. The polycarbonate resin composition according to any one of 1 to 8 above, wherein the notched Charpy impact strength according to ISO179 is 20 kJ / m ² or more.
10. A molded product made of the polycarbonate resin composition according to any one of 1 to 9 above.

The antibacterial polycarbonate resin composition of the present invention has high transparency, high antibacterial property, high impact resistance, heat resistance, moisture heat resistance, and chemical resistance in a well-balanced manner.
An aromatic polycarbonate resin (A) having a viscosity average molecular weight of 17,000 to 28,000, and a thermoplastic resin having a tensile elasticity of 1.0 to 2.5 GPa, which is soft and has a refractive index at the same level as that of the aromatic polycarbonate resin (A). By combining (B) and the antibacterial inorganic oxide (C), both the impact resistance and the transparency of the aromatic polycarbonate resin (A) are made higher, and the aromatic polycarbonate resin (A) has excellent antibacterial properties. It is possible to obtain a polycarbonate resin composition having excellent heat resistance, moisture heat resistance, and chemical resistance.

It is a side view which shows the shape of the jig for three-point bending load used for the evaluation of the chemical resistance in an Example.

Hereinafter, the present invention will be described in detail by showing embodiments and examples, but the present invention is not limited to the embodiments and examples shown below.

The antibacterial polycarbonate resin composition of the present invention has a tensile elastic modulus of 1.0 to 2.5 GPa according to ISO527-1.2 with respect to 100 parts by mass of the aromatic polycarbonate resin (A) having a viscosity average molecular weight of 17,000 to 28,000. 5 to 80 parts by mass of a thermoplastic resin (B) other than the aromatic polycarbonate resin (A) having a modulus of refraction according to ISO489 of 1.45 to 1.59, and at least one Ag, Zn, Zr or Cu element. It contains 0.1 to 2.5 parts by mass of the inorganic oxide (C) contained therein, and is characterized by having a haze value of 20% or less on a plate having a thickness of 2 mm.

[Aromatic Polycarbonate Resin (A)]
The type of the aromatic polycarbonate resin (A) used in the polycarbonate resin composition of the present invention is not limited, and only one type may be used, and two or more types may be used in any combination and any ratio. It may be used together.
The aromatic polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the general formula:-[-O-X-OC (= O)-]-. In the formula, X is an aromatic hydrocarbon, but a heteroatom or an X having a heterobond introduced may be used to impart various properties.

The specific type of the aromatic polycarbonate resin is not limited, and examples thereof include an aromatic polycarbonate polymer obtained by reacting an aromatic dihydroxy compound with a carbonate precursor. At this time, in addition to the aromatic dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting with cyclic ether using carbon dioxide as a carbonate precursor may also be used. Further, the aromatic polycarbonate polymer may be linear or branched. Further, the aromatic polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, as the copolymer, various copolymer forms such as a random copolymer and a block copolymer can be selected. Usually, such an aromatic polycarbonate polymer is a thermoplastic resin.

Examples of aromatic dihydroxy compounds as raw material monomers for aromatic polycarbonate resins are as follows.
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl;

2,2'-Dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1 , 7-Dihydroxynaphthalene, 2,7-dihydroxynaphthalene and other dihydroxynaphthalene;

2,2'-Dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxydiaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-Bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-Bis (3-methyl-4-hydroxyphenyl) propane,
2,2-Bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-Hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-Bis (4-hydroxy-3,5-dimethylphenyl) propane,
2,2-Bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-Hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α'-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-Bis [2- (4-Hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,2-bis (4-hydroxyphenyl) ethane,
1,1-Bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-Bis (4-hydroxyphenyl) butane,
2,2-Bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-Bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-Bis (4-hydroxyphenyl) octane,
4,4-Bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,10-Bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,4-Bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

Cardo-structure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;
Dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;
Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;
Dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; and the like.

Among these, bis (hydroxyaryl) alkanes are preferable, bis (4-hydroxyphenyl) alkanes are more preferable, and 2,2-bis (4-hydroxyphenyl) propane (that is, from the viewpoint of impact resistance and heat resistance). , Bisphenol A) is particularly preferred.
As the aromatic dihydroxy compound, one type may be used, or two or more types may be used in any combination and ratio.

Among the monomers used as raw materials for aromatic polycarbonate resins, examples of carbonate precursors include carbonyl halides and carbonate esters. As the carbonate precursor, one kind may be used, or two or more kinds may be used in any combination and ratio.

Specific examples of the carbonyl halide include phosgene; haloformates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds.

Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditril carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate form of dihydroxy compound, monocarbonate form of dihydroxy compound, and cyclic carbonate. Examples thereof include carbonates of dihydroxy compounds such as.

-Method for producing aromatic polycarbonate resin The method for producing an aromatic polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, particularly suitable of these methods will be specifically described.

Interfacial polymerization method First, a case where an aromatic polycarbonate resin is produced by an interfacial polymerization method will be described.
In the interfacial polymerization method, the pH is usually kept at 9 or higher in the presence of an organic solvent and an alkaline aqueous solution inert to the reaction, and the dihydroxy compound is reacted with a carbonate precursor (preferably phosgene), and then the polymerization catalyst is used. An aromatic polycarbonate resin is obtained by performing interfacial polymerization in the presence. If necessary, a molecular weight modifier (termination inhibitor) may be present in the reaction system, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

The dihydroxy compound and carbonate precursor are as described above. It is preferable to use phosgene among the carbonate precursors, and the method using phosgene is particularly called the phosgene method.

Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; and aromatic hydrocarbons such as benzene, toluene and xylene. Be done. As the organic solvent, one type may be used, or two or more types may be used in any combination and ratio.

Examples of the alkaline compound contained in the alkaline aqueous solution include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium hydrogen carbonate, and alkaline earth metal compounds, among which sodium hydroxide and water are used. Potassium oxide is preferred. As the alkaline compound, one kind may be used, or two or more kinds may be used in any combination and ratio.

The concentration of the alkaline compound in the alkaline aqueous solution is not limited, but is usually used in an amount of 5 to 10% by mass in order to control the pH in the alkaline aqueous solution of the reaction to 10 to 12. Further, for example, when injecting phosgene, the molar ratio of the bisphenol compound to the alkaline compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Above all, it is preferably 1: 2.0 or more, and usually 1: 3.2 or less, and above all, 1: 2.5 or less is preferable.

Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine and trihexylamine; and alicyclic such as N, N'-dimethylcyclohexylamine and N, N'-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N'-dimethylaniline, N, N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. ; Ppyridine; a salt of guanidine; etc. As the polymerization catalyst, one kind may be used, or two or more kinds may be used in any combination and ratio.

Examples of the molecular weight modifier include aromatic phenols having a monovalent phenolic hydroxyl group; fatty alcohols such as methanol and butanol; mercaptans; phthalic acid imides, etc. Among them, aromatic phenols are preferable. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long-chain alkyl-substituted phenol. Substituted phenols; vinyl group-containing phenols such as isopropenylphenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; and the like.
As the molecular weight adjusting agent, one type may be used, or two or more types may be used in combination in any combination and ratio.

The amount of the molecular weight modifier used is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, relative to 100 mol of the dihydroxy compound. By setting the amount of the molecular weight modifier used in this range, the thermal stability and hydrolysis resistance of the resin composition can be improved.

The order in which the reaction substrate, reaction medium, catalyst, additives and the like are mixed at the time of the reaction is arbitrary as long as a desired aromatic polycarbonate resin can be obtained, and an appropriate order may be set arbitrarily. For example, when phosgene is used as the carbonate precursor, the molecular weight modifier can be mixed at any time from the reaction (phosgenation) between the dihydroxy compound and phosgene to the start of the polymerization reaction.
The reaction temperature is usually 0 to 40 ° C., and the reaction time is usually several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

Melt transesterification method Next, a case where the aromatic polycarbonate resin is produced by the melt transesterification method will be described.
In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditril carbonate and the like. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type of carbonic acid diester may be used, and 2 or more types may be used in arbitrary combination and ratio.

The ratio of the dihydroxy compound to the carbonic acid diester is arbitrary as long as the desired aromatic polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound, particularly 1.01 mol. It is more preferable to use the above. The upper limit is usually 1.30 mol or less. By setting it in such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

In aromatic polycarbonate resins, the amount of hydroxyl groups at the ends tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. Therefore, the amount of terminal hydroxyl groups may be adjusted as necessary by any known method. In the transesterification reaction, usually, an aromatic polycarbonate resin having an adjusted amount of terminal hydroxyl groups can be obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound; the degree of decompression during the transesterification reaction and the like. By this operation, the molecular weight of the normally obtained aromatic polycarbonate resin can also be adjusted.

When the mixing ratio of the carbonic acid diester and the dihydroxy compound is adjusted to adjust the amount of terminal hydroxyl groups, the mixing ratio is as described above.
Further, as a more positive adjustment method, there is a method of separately mixing a terminal terminator at the time of reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters and the like. In addition, one kind of terminal terminator may be used, or two or more kinds may be used in any combination and ratio.

When producing an aromatic polycarbonate resin by the transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Above all, for example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. Further, as an auxiliary, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine-based compound may be used in combination. As the transesterification catalyst, one type may be used, or two or more types may be used in any combination and ratio.

In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, the melt polycondensation reaction may be carried out under the above conditions while removing by-products such as aromatic hydroxy compounds.

The melt polycondensation reaction can be carried out by either a batch method or a continuous method. In the case of batch method, the order of mixing the reaction substrate, reaction medium, catalyst, additives and the like is arbitrary as long as a desired aromatic polycarbonate resin can be obtained, and an appropriate order may be set arbitrarily. However, above all, considering the stability of the aromatic polycarbonate resin and the like, it is preferable to carry out the melt polycondensation reaction in a continuous manner.

In the melt transesterification method, a catalyst deactivating agent may be used if necessary. As the catalyst deactivating agent, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. As the catalyst deactivating agent, one type may be used, or two or more types may be used in combination in any combination and ratio.

The amount of the catalyst deactivating agent used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, with respect to the alkali metal or alkaline earth metal contained in the ester exchange catalyst. It is preferably 5 equivalents or less. Further, it is usually 1 ppm or more, and usually 100 ppm or less, preferably 20 ppm or less, with respect to the aromatic polycarbonate resin.

The aromatic polycarbonate resin (A) used has a viscosity average molecular weight (Mv) in the range of 17,000 to 28,000. By using a resin composition having a viscosity average molecular weight (Mv) in such a range, a resin composition having excellent impact resistance and transparency can be obtained. If the Mv is lower than 17,000, the impact resistance is insufficient, and if it exceeds 28,000, uniform dispersion with the thermoplastic resin (B) becomes difficult, and the transparency of the resin composition tends to deteriorate.
The viscosity average molecular weight (Mv) is preferably 18,000 or more, more preferably 19000 or more, still more preferably 20,000 or more, preferably 27,000 or less, and more preferably 26,000 or less.
Two or more kinds of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, aromatic polycarbonate resins having a viscosity average molecular weight outside the above range may be mixed and used in the above range. It may be adjusted to.

The viscosity average molecular weight [Mv] is defined as the ultimate viscosity [η] (unit: dl / g) at a temperature of 25 ° C. using a Ubbelohde viscometer using methylene chloride as a solvent. , Η = 1.23 × 10 ^-4 Mv ^0.83 means a value calculated from. The ultimate viscosity [η] is a value calculated by the following formula by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

The terminal hydroxyl group concentration of the aromatic polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, and more preferably 600 ppm or less. Thereby, the retention heat stability and the color tone of the aromatic polycarbonate resin can be further improved. Further, the lower limit thereof is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly in the aromatic polycarbonate resin produced by the melt transesterification method. As a result, it is possible to suppress a decrease in molecular weight and further improve the mechanical properties of the resin composition.

The unit of the terminal hydroxyl group concentration is the mass of the terminal hydroxyl group expressed in ppm with respect to the mass of the aromatic polycarbonate resin. The measuring method is colorimetric quantification by the titanium tetrachloride / acetic acid method (method described in Macromol. Chem. 88 215 (1965)).

The aromatic polycarbonate resin is not limited to the embodiment containing only one type of polycarbonate resin, and includes, for example, an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. It may be used in combination with an alloy (mixture) of an aromatic polycarbonate resin and another thermoplastic resin.

[Thermoplastic resin (B)]
The polycarbonate resin composition of the present invention has a tensile elastic modulus of 1.0 to 2.5 GPa according to ISO527-1.2 and a refractive index of 1.45 to 1.59 according to ISO489, other than the aromatic polycarbonate resin (A). Contains the thermoplastic resin (B) of. By containing a thermoplastic resin (B) other than the aromatic polycarbonate resin (A) having a tensile elasticity and a refractive index in such a range in combination with the aromatic polycarbonate resin (A), the impact resistance of the resin composition is obtained. By improving the properties and making the refractive index close to the refractive index (1.584) of the aromatic polycarbonate resin (A), it is possible to obtain an excellent transparency.
The tensile elastic modulus of the thermoplastic resin (B) is preferably 1.1 GPa or more, more preferably 1.2 GPa or more, still more preferably 1.3 GPa or more, particularly preferably 1.4 GPa or more, and preferably 2.4 GPa or more. Below, it is more preferably 2.3 GPa or less, still more preferably 2.2 GPa or less, particularly preferably 2.1 GPa or less, 2.0 GPa or less, 1.9 GPa or less, 1.8 GPa or less, and 1.7 GPa or less.

The thermoplastic resin (B) is not limited as long as it is a thermoplastic resin other than the aromatic polycarbonate resin (A) that satisfies the tensile elasticity and the refractive index, but for example, a thermoplastic polyester resin and a methyl methacrylate-based resin (for example). , Polymethylmethacrylate, Methylmethacrylate-phenylmethacrylate copolymer resin) and the like.
Further, other than the aromatic polycarbonate resin (A), an aliphatic polycarbonate resin satisfying the above-mentioned tensile elastic modulus and refractive index can also be preferably used. The aliphatic polycarbonate resin is made from an aliphatic dihydroxy compound, and typical examples thereof include 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and the like. 1,7-Heptanediol, 1,8-octanediol, 1,4-cyclohexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10 -Includes decanediol and the like. Further, those using a dihydroxy compound having a cyclic ether structure such as isosorbide and isomannide as a raw material are also preferable.

As the thermoplastic resin (B), a thermoplastic polyester resin is preferable, and an amorphous polyester resin is particularly preferable.
Amorphousity of an amorphous polyester resin means that it does not show a clear melting point (Tm) when measured by a differential scanning calorimeter (DSC).

As the amorphous polyester resin, an alicyclic diol and / or an amorphous polyester resin having a structural unit derived from a diol having a cyclic acetal skeleton is preferable.
Examples of the alicyclic diol include 2,2,4,4-tetramethyl-1,3-cyclobutanediol (which may be cis, trans, or a mixture thereof), 1,4-cyclohexanedimethanol (or). Mixtures of 1,3- and 1,4-cyclohexanedimethanol, cis, trans, or mixtures thereof) are preferred.

式（１）中、Ｒ^１及びＲ^２はそれぞれ独立して、炭素数が１～１０の脂肪族炭化水素基、炭素数が３～１０の脂環式炭化水素基または炭素数が６～１０の芳香族炭化水素基を示す。 As the diol having a cyclic acetal skeleton, a diol represented by the following general formula (1) is preferably mentioned.

In formula (1), R ¹ and R ² are independent, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms. Shows the aromatic hydrocarbon group of.

In the above general formula (1), R ¹ and R ² are independent of each other and have an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and a carbon number of carbon atoms. A hydrocarbon group selected from the group consisting of 6-10 aromatic hydrocarbon groups, preferably a methylene group, an ethylene group, a propylene group, a butylene group or structural isomers thereof, such as a dimethylethylenel group. It is an isopropylene group and an isobutylene group.
Examples of the diol compound having a cyclic acetal skeleton of the general formula (1) include 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4 in which ^R1 and ^R2 are dimethylethylenel groups. , 8,10-Tetraoxaspiro [5.5] undecane is particularly preferred.

The composition ratio of the alicyclic diol and the diol component having a cyclic acetal skeleton is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, and further, when the total mol% of the diol component is 100 mol%. It is preferably 30 to 100 mol%.

The amorphous polyester resin may contain other diol components other than the alicyclic diol and the diol having a cyclic acetal skeleton. The content of the other diol is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70, when the total number of moles of the diol component of the amorphous polyester resin is 100 mol%. It is less than mol%.
Examples of other diols include diols containing 2 to 16 carbon atoms, such as ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, and 1,4-butane. Examples thereof include diol, 1,5-pentanediol, 1,6-hexanediol or a mixture thereof.

Examples of the dicarboxylic acid component of the amorphous polyester resin include alicyclic dicarboxylic acids and aromatic dicarboxylic acids, with aromatic dicarboxylic acids being preferred. The aromatic dicarboxylic acid is preferably terephthalic acid, and the amount thereof is preferably 80 mol% or more, more preferably 90 mol% or more. In addition to terephthalic acid, the dicarboxylic acid component can have up to less than 50 mol% of other dicarboxylic acids.
Examples of aromatic dicarboxylic acids other than terephthalic acid include isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, 4, Examples thereof include 4'-stillbenzicarboxylic acid.
Further, it is possible to contain an aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid and azalen acid, but the amount thereof is preferably 10 mol% or less.

The ultimate viscosity of the amorphous polyester resin is preferably in the range of 0.3 to 1.2 dl / g, more preferably 0.5 to 1.0 dl / g, and further preferably 0.7 to 0.9 dl / g. be. When the ultimate viscosity is in the above range, the moldability and strength are excellent.
In the present invention, the ultimate viscosity [η] of the polyester resin is measured at 25 ° C. in a 1: 1 (mass ratio) mixed solvent of 1,1,2,2-tetrachloroethane and phenol.

Particularly preferred as the amorphous polyester resin are terephthalic acid residues, 1,4-cyclohexanedimethanol (hereinafter also referred to as “CHDM”) residues, and 2,2,4,4-tetramethyl-1, A polyester resin containing a 3-cyclobutanediol (hereinafter, also referred to as “TMCD”) residue is preferable.
The total ratio of CHDM residues and TMCD residues to all diol residues is preferably 85 mol% or more, particularly 90 to 100 mol%, particularly 95 to 100 mol%, from the viewpoint of transparency and heat resistance. ..
Further, it is preferable that the ratio of CHDM residues to the total of 100 mol% of CHDM residues and TMCD residues is 10 to 90 mol%, and the ratio of TMCD residues is 90 to 10 mol%. More preferably, the proportion is 20-85 mol% and the proportion of TMCD residues is 15-80 mol%, the proportion of CHDM residues is 30-80 mol% and the proportion of TMCD residues is 20-70 mol%. It is particularly preferable to have.

As such an amorphous polyester resin, a commercially available product can be used, and for example, it can be selected and used from the trade name "Tritan" series manufactured by Eastman Chemical Company.

Further, as the amorphous polyester resin, particularly preferable is a carboxylic acid unit in which the carboxylic acid constituent unit is selected from at least one of a terephthalic acid residue, an isophthalic acid residue, and a 1,4-cyclohexanedicarboxylic acid residue. The constituent unit derived from the diol is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (hereinafter referred to as "spiroglycol"). It is a polyester resin containing 10 to 100 mol% of the total diol constituent unit and 90 to 0 mol% of ethylene glycol or 1,4-cyclohexanedimethanol in the total diol constituent unit.

The constituent unit derived from spiroglycol is preferably 10 to 80 mol%, more preferably 30 to 75 mol% of the total diol constituent unit. The structural unit derived from ethylene glycol is preferably 0 to 65 mol%.
The carboxylic acid constituent unit preferably has 90 to 100 mol% of terephthalic acid residues.

As such an amorphous polyester resin, a commercially available product can be used, and for example, it can be selected and used from the trade name "Artesta" series manufactured by Mitsubishi Gas Chemical Company.

The content of the thermoplastic resin (B) is 5 to 80 parts by mass, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and preferably 20 parts by mass or more, based on 100 parts by mass of the aromatic polycarbonate resin (A). Is 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 55 parts by mass or less, and particularly preferably 50 parts by mass or less. By containing it in such a range, impact resistance and transparency, as well as heat resistance, moisture heat resistance, and chemical resistance can be improved in a well-balanced manner.

[Inorganic oxide (C)]
The polycarbonate resin composition of the present invention contains an inorganic oxide (C) containing at least one Ag, Zn, Zr or Cu element. The inorganic oxide (C) is an antibacterial inorganic oxide particle containing at least one of Ag, Zn, Zr or a Cu element (atom), and such an inorganic oxide (C) can be used as an aromatic polycarbonate resin (Aromatic polycarbonate resin). By containing A) and the thermoplastic resin (B) in combination, an antibacterial resin composition having excellent transparency can be obtained while maintaining the impact resistance of the resin composition.

The inorganic oxide (C) may contain at least one of Ag, Zn, Zr or a Cu element (atom), and the type thereof is not particularly limited. Further, the form of Ag, Zn, Zr or Cu element (atom) is not particularly limited, and includes, for example, a metal, an ion, an oxide, a salt (including a complex) and the like. The inorganic oxide (C) is preferably an inorganic oxide having an elution ability of Ag, Zn, Zr or Cu ions.
For example, examples of the case of silver include silver particles that slowly release silver ions and an antibacterial agent of an inorganic oxide containing silver.

The Ag, Zn, Zr, and Cu elements (atoms) may be used alone or in combination of two or more. Among these, Ag, Zn and Cu are preferable in that they have excellent antibacterial properties, Ag-based, Ag-Zn-based, Zn-based and Ag-Cu-based are preferable, and Ag or a combination of Ag and Zn is preferable.

Examples of the inorganic oxide having antibacterial activity include oxides of Ag, Zn, Zr or Cu or composite oxides thereof, such as silver oxide, zinc oxide, zirconium oxide, copper oxide, and composite oxides thereof. Is preferably mentioned. Further, copper oxide sol, silver oxide sol, zinc sol, zirconia sol and the like may be used.

As the antibacterial inorganic oxide (C), one in which a metal, ion, metal oxide, metal salt or the like of Ag, Zn, Zr or Cu is supported on an inorganic oxide carrier can also be used. The metal salt is a nitrate of Ag, Zn, Zr or Cu, a sulfate, a halide and the like.
Examples of the inorganic oxide carrier include glass, ceramics, silica, silica gel, zinc oxide, zirconium oxide, copper oxide, titanium oxide, zeolite, clay minerals and the like. These carriers are preferably in the form of particles, particularly those in the form of fine particles.

The inorganic oxide (C) preferably has a refractive index of 1.45 to 1.59 according to ISO489. When the refractive index is in such a range, the transparency of the resin composition can be further improved.

As the antibacterial inorganic oxide (C), silver or silver-zinc supported on glass, ceramics or the like is particularly preferable.

The antibacterial inorganic oxide (C) is preferably in the form of particles, and the average particle size thereof is preferably 0.1 to 20 μm, more preferably 0.5 μm or more, still more preferably 1 μm or more, and more preferably. Is 15 μm or less, more preferably 13 μm or less. When the average particle size is in such a range, the antibacterial effect is high, the blending amount can be made smaller, and the transparency of the resin composition can be made better.

The content of Ag, Zn, Zr, and Cu element (atom) in the inorganic oxide (C) is preferably 0.1 to 10% by mass with respect to 100% by mass of the total mass of the inorganic oxide (C).

The content of the inorganic oxide (C) is 0.1 to 2.5 parts by mass, preferably 0.2 parts by mass or more, and more preferably 0. parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). It is preferably 3 parts by mass or more, particularly 0.4 parts by mass or more, preferably 2 parts by mass or less, more preferably 1.8 parts by mass or less, and further preferably 1.5 parts by mass or less. By containing it in such a range, it is possible to maintain impact resistance while having excellent transparency, and to maintain a good balance of heat resistance, moisture heat resistance, and chemical resistance.

[Phosphorus stabilizer (D)]
The polycarbonate resin composition of the present invention preferably contains a phosphorus-based stabilizer. Any known phosphorus-based stabilizer can be used. Specific examples are oxo acids of phosphorus such as phosphoric acid, phosphonic acid, phosphite, phosphinic acid and polyphosphate; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, potassium pyrophosphate, acidic calcium pyrophosphate; phosphoric acid. Phosphates of Group 1 or Group 2 C metals such as potassium, sodium phosphate, cesium phosphate, zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc., but also organic phosphite compounds and Organic phosphate compounds are preferred, with organic phosphate compounds being particularly preferred.

Examples of the organic phosphite compound include triphenylphosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl-phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and monooctyl. Diphenylphosphite, dioctylmonophenylphosphite, monodecyldiphenylphosphite, didecylmonophenylphosphite, tridecylphosphite, trilaurylphosphite, tristearylphosphite, 2,2-methylenebis (4,6-di- tert-Butylphenyl) octylphosphite and the like can be mentioned.
Specific examples of such an organic phosphite compound include "ADEKA TAB 1178", "ADEKA STAB 2112", "ADEKA STAB HP-10" manufactured by ADEKA, and "JP-351" and "JP-351" manufactured by Johoku Chemical Industry Co., Ltd. Examples thereof include "JP-360", "JP-3CP", and "Irgafos 168" manufactured by BASF Corporation.
The phosphorus-based stabilizer may contain one kind or two or more kinds in any combination and ratio.

式中、Ｒ^１はアルキル基又はアリール基を表す。ｎは１～２の整数を表す。なお、ｎが１のとき、２つのＲ^１は同一でも異なっていてもよい。 As the organic phosphate compound, an organic phosphate represented by the following general formula is preferable.

In the formula, R ¹ represents an alkyl group or an aryl group. n represents an integer of 1 to 2. When n is ¹ , the two R1s may be the same or different.

In the above general formula, R ¹ represents an alkyl group or an aryl group. R ¹ is more preferably an alkyl group having 1 or more carbon atoms, preferably 2 or more carbon atoms, usually 30 or less, preferably 25 or less, or an aryl group having 6 or more carbon atoms and usually 30 or less carbon atoms. , R ¹ is preferably an alkyl group rather than an aryl group. When two or more R ^1s are present, the R ^1s may be the same or different from each other.

Preferred compounds represented by the above general formula include long-chain alkyl acid phosphate compounds in which R ¹ has 8 to 30 carbon atoms. Specific examples of the long-chain alkyl group having 8 to 30 carbon atoms include an octyl group, a 2-ethylhexyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, a dodecyl group, a tridecyl group, an isotridecyl group and a tetradecyl group. Examples thereof include a group, a hexadecyl group, an octadecyl group, an eicosyl group, a triacontyl group and the like.

Examples of long-chain alkyl acid phosphates include octadecyl acid phosphate (ie, stearyl acid phosphate), 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, and phenyl acid phosphate. , Nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate. , Di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distealyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate and the like.

Among these, octadecyl acid phosphate (that is, stearyl acid phosphate), mono-, and di-stearyl acid phosphate have high heat resistance, so that decomposition gas is less generated at the resin processing temperature, and compatibility with the resin is achieved. Since it has good dispersibility in the resin, it is preferable because there is little bleeding out to the surface of the processed resin product. This product is commercially available under the trade name "ADEKA STAB AX-71" manufactured by ADEKA.

As the organic phosphate compound, an organic phosphate metal salt can also be suitably used. Specific examples thereof include a mixture of a zinc salt of distearyl acid phosphate and a zinc salt of monostearyl acid phosphate, mono-, and di-stearyl acid phosphate and the like.
Specific examples of such an organic phosphate metal salt include "JP-518Zn" manufactured by Johoku Chemical Industry Co., Ltd., and "AX-71" manufactured by ADEKA as a mono- and di-stearyl acid phosphate. Can be mentioned.

Among the above, mono or di-stearyl acid phosphate and a mixture thereof exhibit resin stability with a small amount of addition, so that appearance changes such as whitening in a moist heat environment are unlikely to occur, which is preferable.

The content of the phosphorus-based stabilizer is preferably 0.01 to 0.15 parts by mass, more preferably 0.015 parts by mass or more, and more preferably, with respect to 100 parts by mass of the aromatic polycarbonate resin (A). It is preferably 0.14 parts by mass or less, and more preferably 0.13 parts by mass or less. When the content of the phosphorus-based stabilizer is within the above range, a good heat stabilizing effect is exhibited.

[Phenolic stabilizer]
It is also preferable that the polycarbonate resin composition of the present invention contains a phenolic stabilizer. Examples of the phenol-based stabilizer include hindered phenol-based antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5-di-) tert-Butyl-4-hydroxyphenylpropionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxy) Phenyl] methyl] phosphate, 3,3', 3 ", 5,5', 5" -hex-tert-butyl-a, a', a "-(mesitylen-2,4,6-triyl) tri-p -Cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene bis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -Trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2- Ilamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate and the like can be mentioned.

Of these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferable. .. Specific examples of such phenolic antioxidants include, for example, "Irganox 1010" and "Irganox 1076" manufactured by BASF, "ADEKA STAB AO-50" and "ADEKA STAB AO-60" manufactured by ADEKA. Can be mentioned.
The phenolic stabilizer may contain one kind or two or more kinds in any combination and ratio.

The content of the phenolic stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, based on 100 parts by mass of the aromatic polycarbonate resin (A). It is preferably 0.5 parts by mass or less. If the content of the phenolic stabilizer is less than the lower limit of the above range, the effect as the phenolic stabilizer may be insufficient, and the content of the phenolic stabilizer exceeds the upper limit of the above range. In that case, the effect may reach a plateau and become uneconomical.

[Release agent]
It is also preferable that the polycarbonate resin composition of the present invention contains a mold release agent. Examples of the mold release agent include an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a polysiloxane-based silicone oil.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, the preferred aliphatic carboxylic acid is a monovalent or divalent carboxylic acid having 6 to 36 carbon atoms, and an aliphatic saturated monovalent carboxylic acid having 6 to 36 carbon atoms is more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, araquinic acid, bechenic acid, lignoseric acid, cellotic acid, melissic acid, tetrariacontanic acid, montanic acid and adipine. Acids, azelaic acid and the like can be mentioned.

As the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol, for example, the same one as the above-mentioned aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the term aliphatic is used as a term including an alicyclic compound.

Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Can be mentioned.

The above ester may contain an aliphatic carboxylic acid and / or an alcohol as impurities. Further, the above ester may be a pure substance or a mixture of a plurality of compounds. Further, as the aliphatic carboxylic acid and the alcohol which are combined to form one ester, one kind may be used, or two or more kinds may be used in any combination and ratio.

Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monosteer. Examples thereof include rate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, fisher-tropus wax, α-olefin oligomer having 3 to 12 carbon atoms and the like. Here, the aliphatic hydrocarbon also includes an alicyclic hydrocarbon. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but a mixture of constituents and various molecular weights can be used as long as the main component is within the above range.

Examples of the polysiloxane-based silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

The above-mentioned mold release agent may contain one kind or two or more kinds in any combination and ratio.

The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 2 parts by mass, based on 100 parts by mass of the aromatic polycarbonate resin (A). Is 1 part by mass or less. If the content of the release agent is less than the lower limit of the above range, the effect of the release property may not be sufficient, and if the content of the release agent exceeds the upper limit of the above range, the hydrolysis resistance There is a possibility that the mold will be reduced and the mold will be contaminated during injection molding.

[Other ingredients]
The polycarbonate resin composition of the present invention may contain other components in addition to those described above, if necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resin, various resin additives, and the like. In addition, 1 type may be contained in the other component, and 2 or more types may be contained in arbitrary combinations and ratios.

-Other resins Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate; polystyrene resin, high impact polystyrene resin (HIPS), and acrylonitrile-styrene copolymer (AS resin). ) And the like; polyolefin resin such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; polymethacrylate resin and the like.

In addition, 1 type may be contained in the other resin, and 2 or more types may be contained in arbitrary combinations and ratios.
However, when the other resin is contained, the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further 5 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin (A). Above all, it is preferably 3 parts by mass or less, particularly preferably 1 part by mass or less.

-Resin additive Examples of the resin additive include an ultraviolet absorber, a dye pigment, an antistatic agent, an anti-fog agent, an anti-blocking agent, a fluidity improver, a plasticizer, and a dispersant. In addition, 1 type may be contained in the resin additive, and 2 or more types may be contained in arbitrary combinations and ratios.

[Manufacturing method of polycarbonate resin composition]
The method for producing the polycarbonate resin composition of the present invention is not limited, and a known method for producing the polycarbonate resin composition can be widely adopted.
To give a specific example, the above-mentioned essential ingredients and other ingredients to be blended as needed are premixed using various mixers such as a tumbler and a Henschel mixer, and then a Banbury mixer, a roll, a brabender, and the like. Examples thereof include a method of melt-kneading with a mixer such as a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader.

Further, for example, the polycarbonate resin composition of the present invention is produced without mixing each component in advance, or by mixing only a part of the components in advance, supplying the mixture to an extruder using a feeder, and melt-kneading the mixture. You can also do it.
Further, for example, a resin composition obtained by premixing some components and supplying them to an extruder to be melt-kneaded is used as a masterbatch, and this masterbatch is mixed with the remaining components again and melt-kneaded. The polycarbonate resin composition of the present invention can also be produced.
Further, for example, when a component that is difficult to disperse is mixed, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance and kneaded with the solution or dispersion to disperse the component. It can also enhance sex.

The polycarbonate resin composition of the present invention has high transparency, and exhibits a haze value of 20% or less on a plate having a thickness of 2 mm formed by using the polycarbonate resin composition. The haze value is preferably 15% or less, more preferably 12% or less, still more preferably 10% or less, and the lower limit thereof is preferably 2% or more, further preferably 3% or more.
The details of the method for measuring the haze value are as described in the examples, but the obtained plate having a thickness of 2 mm and a length of 50 mm × a width of 50 mm is compliant with JIS K7136 and JIS K7361 and is a haze meter with a D65 light source. It is performed in a 10 ° field of view.

The polycarbonate resin composition of the present invention has high impact resistance and can achieve a notched Charpy impact strength of ISO179, preferably 20 kJ / m ² or more. The Charpy impact strength is more preferably 25 kJ / m ² or more, still more preferably 30 kJ / m ² or more, especially 35 kJ / m ² or more, 40 kJ / m ² or more, 45 kJ / m ² or more, 50 kJ / m ² or more, 55 kJ. / M ² or more, especially 60 kJ / m ² or more.

As a method for producing the molded product, any molding method generally adopted for the polycarbonate resin composition can be adopted. For example, an injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas assist, a molding method using a heat insulating mold, and a rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermal molding method, rotary molding method, laminated molding method, press molding method, A blow molding method and the like can be mentioned, and a molding method using a hot runner method can also be used. Among them, injection molding methods such as an injection molding method, an ultra-high speed injection molding method, and an injection compression molding method are preferable.

[Molded product]
Examples of molded bodies include parts such as electrical / electronic equipment, OA equipment, information terminal equipment, mechanical parts, home appliances, vehicle parts, building materials, various containers, leisure goods / miscellaneous goods, and lighting equipment. It is particularly suitable for products and parts that can be touched by human hands, such as miscellaneous goods, switches and buttons for general household appliances, elevator operation buttons, buttons and front covers for amusement machines such as pachinko and slot machines, leisure goods and playset. Can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not construed as being limited to the following examples.
The components used in the examples and comparative examples are as shown in Table 1 below.

(Examples 1 to 15, Comparative Examples 1 to 12)
[Manufacturing of resin pellets]
Each component listed in Table 1 above is blended in the ratio (mass ratio) shown in Table 2 and below, and kneaded with a twin-screw extruder (“TEM26SX” manufactured by Shibaura Machine Co., Ltd.) at a barrel temperature of 280 ° C. and 200 rpm. , Polycarbonate resin composition pellets were produced at a discharge rate of 20 kg / hr.

[Molding condition]
The obtained pellets are dried at 80 ° C. for 5 hours, and then injection molded using an injection molding machine (“J85AD” manufactured by Japan Steel Works, Ltd.) under the conditions of a resin temperature of 280 ° C. and a mold temperature of 80 ° C. An ASTM D790 bending test piece was obtained.

[Chemical resistance test]
Using the jig to which the three-point bending load shown in FIG. 1 can be applied, the ASTM D790 bending test piece 1 is attached to the lower center of the test piece mounting jig 2 with ethanol applied, and the test piece mounting cure. The bending amount (deformation rate%) can be adjusted by attaching a caulking adjusting cylinder 3 for adjusting the bending amount to the tool 2 and fixing it with a thumbscrew 4.
After applying ethanol to the center of the test piece in the length direction, bend it at three points so that the deformation rate is 1%, leave it to stand in a room temperature of 23 ° C. and 50% Rh environment for 48 hours, and then place the ethanol-coated part in an optical microscope. And confirmed the presence or absence of cracks.

[Chemical resistance evaluation]
Chemical resistance was evaluated according to the following criteria.
A when no cracks occur.
Cracks occur, and the crack length is less than 5 mm.
The case where cracks were generated and the crack length of any of them was 5 mm or more was defined as C.

[Preparation of plates for antibacterial evaluation and HAZE measurement]
The obtained pellets are dried at 80 ° C. for 5 hours, and then injection molded using an injection molding machine (“J85AD” manufactured by Japan Steel Works) under the conditions of a resin temperature of 280 ° C. and a mold temperature of 80 ° C., 2 mm. After obtaining a plate having a thickness of 100 mm in length × 100 mm in width, the plate was cut into a thickness of 2 mm and having a thickness of 50 mm in length × 50 mm in width to obtain a plate for antibacterial evaluation and HAZE measurement.

[Antibacterial evaluation]
Using the obtained 2 mm thickness, length 50 mm × width 50 mm, the viable cell count of Escherichia coli after 24 hours under a room temperature of 35 ° C. and a 90% Rh environment was confirmed by the method described in JIS Z2801, and the viable cells were confirmed after 24 hours. If it does not increase to the number, it is evaluated as 〇, and if it increases, it is evaluated as ×.

[Transparency: HAZE measurement]
The obtained 2 mm thick, length 50 mm x width 50 mm plate conforms to JIS K7136 and JIS K7361 and is a haze meter "NDH4000" manufactured by Nippon Denshoku Industries Co., Ltd., with a D65 light source and a HAZE value (%) in a 10 ° field of view. ) Was measured.

[Evaluation of moisture resistance]
The obtained 2 mm thick, 50 mm long × 50 mm wide plate was allowed to stand in a moist heat environment at 85 ° C. and 85% Rh for 100 hours, and the haze value difference (%) before and after that was measured.

[Impact resistance: Charpy impact test with notch]
The obtained pellets are dried at 80 ° C. for 5 hours, and then injection molded using an injection molding machine (“J85AD” manufactured by Japan Steel Works, Ltd.) under the conditions of a resin temperature of 280 ° C. and a mold temperature of 80 ° C., ISO527. The charpy impact strength (unit: kJ / m ² ) was measured after forming the 1 and 2 dumbbell test pieces 1A with a thickness of 3 mm and cutting them into the notched Charpy test piece shape described in ISO179.

[Heat resistance: DTUL measurement (deflection temperature under load, unit: ° C)]
After drying the obtained pellets at 80 ° C. for 5 hours, injection molding was performed under the conditions of a resin temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine “J85AD” manufactured by Japan Steel Works, Ltd., and ISO527-1. , 2 dumbbell test piece 1A type was manufactured with a thickness of 4 mm, cut into the shape of the test piece described in ISO75-2, and DTUL (unit: ° C.) under a 1.8 MPa load was measured by the method described in ISO75-2. ..
The above results are shown in Table 2-5 below.
In the table, "actual n" represents Example n, and "ratio n" represents Comparative Example n.

[Antibacterial evaluation-antibacterial activity value]
Furthermore, the following antibacterial tests were performed on Example 1 and Comparative Example 1.
Using the obtained plate having a thickness of 2 mm and a length of 50 mm and a width of 50 mm, the plate was immersed in water at 50 ° C. for 18 hours (corresponding to the water resistance category 2 of the sustainability standard of the Antibacterial Product Technology Council), and then described in JIS Z2801. By the method, the antibacterial activity value R of Staphylococcus aureus NBRC 12732 after 24 hours under a room temperature of 35 ° C. and a 90% Rh environment was measured.
If the obtained antibacterial activity value R is 2 or more, it is determined to be A, if the antibacterial activity value R is 1 or more and less than 2, it is determined to be B, and if the antibacterial activity value R is less than 1, it is determined to be C.
The results are shown in Table 6 below.

The antibacterial polycarbonate resin composition of the present invention is excellent in high transparency, high antibacterial property, high impact resistance, heat resistance, moisture heat resistance, and chemical resistance. It can be widely and suitably used for parts such as miscellaneous goods, game machines, game machines, and play equipment, and has very high industrial utility.

Claims (10)

With respect to 100 parts by mass of the aromatic polycarbonate resin (A) having a viscosity average molecular weight of 17,000 to 28,000, the tensile elasticity according to ISO527-1.2 is 1.0 to 2.5 GPa and the refractive index according to ISO489 is 1.45 to Inorganic oxide (C) 0 containing 5 to 80 parts by mass of a thermoplastic resin (B) other than the aromatic polycarbonate resin (A), which is 1.59, and at least one Ag, Zn, Zr, or Cu element. An antibacterial polycarbonate resin composition containing 1 to 2.5 parts by mass and having a haze value of 20% or less on a plate having a thickness of 2 mm. The polycarbonate resin composition according to claim 1, further containing 0.01 to 0.15 parts by mass of the phosphorus-based stabilizer (D) with respect to 100 parts by mass of the aromatic polycarbonate resin (A). The polycarbonate resin composition according to claim 1 or 2, wherein the thermoplastic resin (B) is an amorphous thermoplastic polyester resin. The thermoplastic resin (B) is a thermoplastic polyester resin containing a terephthalic acid residue, a 1,4-cyclohexanedimethanol residue, and a 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue. The polycarbonate resin composition according to any one of claims 1 to 3. The thermoplastic resin (B) is a carboxylic acid unit in which the carboxylic acid constituent unit is selected from at least one of a terephthalic acid residue, an isophthalic acid residue, and a 1,4-cyclohexanedicarboxylic acid residue, and is derived from a diol. The constituent unit is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane in an amount of 10 to 100 mol% of all diol constituent units. , And the polycarbonate resin composition according to any one of claims 1 to 3, which is a thermoplastic polyester resin containing ethylene glycol or 1,4-cyclohexanedimethanol in an amount of 90 to 0 mol% in the total diol constituent unit. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the inorganic oxide (C) has a refractive index of 1.45 to 1.59 according to ISO489. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the inorganic oxide (C) is an inorganic oxide having an ability to elute Ag, Zn, Zr or Cu ions. The polycarbonate resin composition according to claim 2, wherein the phosphorus-based stabilizer (D) is a stearyl acid phosphate-based stabilizer. The polycarbonate resin composition according to any one of claims 1 to 8, wherein the ISO179 notched Charpy impact strength is 20 kJ / m ² or more. A molded product made of the polycarbonate resin composition according to any one of claims 1 to 9.

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