KR20120050964A - Housing for portable electronic appliance - Google Patents

Abstract

Content of the polyorganosiloxane block part which has a structural unit of general formula (I) and a structural unit of general formula (II), and contains the structural unit of general formula (II) is 1-30 mass%, 10-100 mass parts of polycarbonate-polyorganosiloxane copolymer (A-1) whose average repeating unit number of the structural unit of this general formula (II) is 70-1000, and a viscosity average molecular weight is 13000-26000. It is a thin, portable electronic device case formed by molding a polycarbonate resin composition containing 0 to 90 parts by mass of an aromatic polycarbonate (A-2) other than 1) in a total amount of 100 parts by mass. .

Description

Portable electronic device case {HOUSING FOR PORTABLE ELECTRONIC APPLIANCE}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a case for storing an electronic device, and more particularly, to a thin, falling impact resistance, which is formed by molding a polycarbonate resin composition comprising a polycarbonate-polyorganosiloxane copolymer having a specific structure. The present invention relates to a portable electronic device case having excellent fluidity and heat resistance.

A resin material is used abundantly in the case of portable electronic devices, such as a portable PC, a portable information terminal (PDA), a mobile telephone, a portable player, and a battery case.

Assuming that the electronic device is accidentally dropped while carrying, in order to protect the internal electronic device, it is necessary to guarantee the impact resistance of the case so as not to cause cracks or destruction to the case.

However, since thermal properties such as impact strength and thermal deformation temperature of resin materials are inferior to those of metal materials, an alloy material such as a thickened molded article such as a case or a blend of resin materials is used, or a plastic material. Attempts have been made to improve the mechanical and thermal properties by filling inorganic fillers or organic fillers into fiber reinforced plastics.

In general, high strength of the case is a very difficult technique in the molding processing of plastic materials, and particularly in the field of injection molding having excellent mass productivity, improvement of the resin material is always desired.

Therefore, impact resistance is considered at the time of selection of a resin material, and especially a material with high impact strength is preferable.

In addition, in injection molding, since residual stress due to molecular orientation deformation or cooling deformation tends to occur in the molded article, when a material having a low heat deformation temperature is used, the residual stress is opened under a high temperature operating environment and the case is deformed. Because of the danger, materials with high heat deflection temperatures are preferred.

As a resin composition for mobile phone cases, what added the rubber component to the polycarbonate for the purpose of impact strength improvement is known (for example, refer patent document 1).

When the polycarbonate-polydimethylsiloxane copolymer having a polydimethylsiloxane (PDMS) moiety having a repeat number n of 100 to 400, specifically n to 150 to 350, of the dimethylsiloxane unit is mixed with glass fibers, the impact resistance is small. It is known that the effect is not obtained when the number n and the number of repetitions n is 100 or less, but there is no description of the PDMS structure or the number of repetitions affecting the impact resistance when excluding the influence of the glass fiber. Even if it is seen, the influence which the repeating number has on impact strength is not seen (for example, refer patent document 2).

It is also known that polycarbonate-polydimethylsiloxane copolymers having a repeating number n of 40 to 60, specifically n of 49, of dimethylsiloxane units exhibit good low-temperature impact properties (see, for example, Patent Document 3). .

Moreover, the method of obtaining the transparent polycarbonate polydimethylsiloxane copolymer which has a PDMS part whose repeat number n of a dimethylsiloxane unit is 50 (for example, refer patent document 4), and the repeat number n of a dimethylsiloxane unit is 0-20. Transparent, flame retardant polycarbonate-polydimethylsiloxane copolymer having a PDMS moiety (see, eg, Patent Document 5), PDMS with a repeating number n of 2 to 500, specifically n of 30 or 150 of the siloxane units The flame retardant resin composition which consists of a polycarbonate polydimethylsiloxane copolymer which has a part is known (for example, refer patent document 6).

However, the polycarbonate resin composition for portable electronic device cases which can be made thin and excellent in fall impact resistance, fluidity | liquidity, and heat resistance is unknown.

Japanese Laid-Open Patent Publication 2006-176612 Japanese Patent No. 2662310 Japanese Patent Publication No. 2006-523243 Japanese Patent Publication No. 2005-535761 Japanese Patent Publication No. 2005-519177 Japanese Patent Application Laid-Open No. 8-81620

The present invention has been made to solve the problems of the prior art, and is formed by molding a polycarbonate resin composition comprising a polycarbonate-polyorganosiloxane copolymer having a specific structure, and has a thin, falling impact resistance, fluidity and heat resistance. An object of the present invention is to provide an excellent portable electronic device case.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the object can be achieved by shape | molding the polycarbonate resin composition containing the polycarbonate polyorganosiloxane copolymer which has a specific structure as a result of earnest research in order to achieve the said objective. .

The present invention has been completed based on these findings.

That is, the present invention,

1. Content of the polyorganosiloxane block part which has a structural unit represented by general formula (I) and the structural unit represented by general formula (II), and contains the structural unit represented by general formula (II) is 1-30 mass. %, 10 to 100 mass of polycarbonate-polyorganosiloxane copolymer (A-1) whose average repeating unit number of the structural unit of the general formula (II) is 70 to 1000, and the viscosity average molecular weight is 13000 to 26000. And a polycarbonate resin composition comprising 0 to 90 parts by mass of an aromatic polycarbonate (A-2) other than (A-1) and a total amount of 100 parts by mass, wherein the portable electronic device case comprises:

[Formula 1]

[In formula, R <^1> and R <^2> is respectively independently a C1-C6 alkyl group or an alkoxy group, X is a single bond, a C1-C8 alkylene group, a C2-C8 alkylidene group, and a C5-C15 A cycloalkylene group, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO _2- , -O- or CO-, R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom or a substituent Represents an alkyl group or an aryl group which may have a, and a and b each independently represent an integer of 0 to 4;

2. The portable electronic device case according to 1 above, which is molded by injection molding;

3. The portable electronic device case according to 2 above, wherein the portable electronic device case has a thickness of 0.5 to 1.5 mm;

4. The portable electronic device case provides the portable electronic device case according to 2 or 3 above, wherein the portable electronic device is a mobile phone.

According to the present invention, by molding a polycarbonate resin composition comprising a polycarbonate-polyorganosiloxane copolymer having a specific structure, the impact strength can be greatly improved without sacrificing fluidity of the polycarbonate, and A portable electronic device case excellent in drop impact resistance, fluidity and heat resistance can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the dimension of the molded article (50 mm x 88 mm, depth 4.5 mm, thickness 1.2 mm) of the mobile telephone model type | mold using the resin composition of Examples 1-7 and Comparative Examples 1 and 2. FIG.

The portable electronic device case of the present invention has a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), and includes a structural unit represented by the general formula (II). Polycarbonate-polyorganosiloxane copolymer (A-) whose content is 1-30 mass%, the average repeating unit number of the structural unit of the general formula (II) is 70-1000, and a viscosity average molecular weight is 13000-26000. 1) The polycarbonate resin composition containing 10-100 mass parts and 0-90 mass parts of aromatic polycarbonates (A-2) other than (A-1) so that a total amount may be 100 mass parts is characterized by the above-mentioned.

[Formula 2]

[In formula, R <^1> and R <^2> is respectively independently a C1-C6 alkyl group or an alkoxy group, X is a single bond, a C1-C8 alkylene group, a C2-C8 alkylidene group, and a C5-C15 A cycloalkylene group, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO _2- , -O- or CO-, R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom or a substituent Represents an alkyl group or an aryl group which may have a, and a and b each independently represent an integer of 0 to 4;

Content of the polyorganosiloxane block part containing the structural unit represented by General formula (II) becomes like this. Preferably it is 1-20 mass%, and if it is less than 1.0 mass%, the effect of drop-resistant impact strength improvement is not enough, and it is 30 mass When it exceeds%, the fall of heat resistance will become large.

In addition, the average number of repeating units of the structural unit of the general formula (II) is preferably 80 to 700, more preferably 80 to 500, and if it is less than 70, the effect of improving the drop resistance impact strength is not sufficient, and it is more than 1000. When the polydimethylsiloxane-polycarbonate copolymer (A-1) is prepared, handling becomes difficult and economy is inferior.

Generally, in order to express fall impact resistance, it is effective that the viscosity average molecular weight of the polycarbonate polyorganosiloxane copolymer (A-1) is large, but when the viscosity average molecular weight becomes large, molding of a thin member such as a portable electronic device case This becomes difficult.

It is also possible to lower the viscosity of the resin composition by increasing the molding temperature, but in that case, the molding cycle becomes longer and the economy is inferior. In addition, if the temperature is too high, the production stability is lowered due to thermal degradation of the resin composition.

Therefore, the viscosity average molecular weight of a polycarbonate polyorganosiloxane copolymer (A-1) becomes like this. Preferably it is 14000-23000, More preferably, it is 15000-22000.

If the viscosity-average molecular weight is less than 13000, the strength of the molded article is not sufficient. If the viscosity-average molecular weight exceeds 26000, the viscosity of the copolymer is increased, and productivity at the time of manufacture is lowered, and molding of the thin film is also difficult.

The polycarbonate resin composition of the present invention is a composition containing the component (A-1) and the component (A-2) so that the total amount is 100 parts by mass, and the content of the polycarbonate-polyorganosiloxane copolymer (A-1) is Preferably it is 50-100 mass parts, More preferably, it is 60-95 mass parts, Content of aromatic polycarbonate (A-2) other than (A-1) becomes like this. Preferably it is 50-0 mass parts, More preferably Is 40-5 parts by mass.

If content of a polycarbonate polyorganosiloxane copolymer (A-1) is less than 10 mass parts, the polyorganosiloxane block part containing the structural unit represented by General formula (II) at the time of component (A-1) manufacture. It is necessary to make the content of at least 30 mass%, in which case the uniformity of the reaction is lowered in the polymerization step at the time of preparation of component (A-1) or the separation of the polymer and the washing water is deteriorated in the washing step of the polymer. Therefore, productivity of component (A-1) falls large.

When content of aromatic polycarbonate (A-2) other than (A-1) exceeds 90 mass parts, content of component (A-1) will be less than 10 mass parts, and it is unpreferable for the said reason.

Next, a polycarbonate polyorganosiloxane copolymer (A-1) is demonstrated.

The polycarbonate-polyorganosiloxane copolymer used in the present invention is a divalent phenol represented by the general formula (1) and a polyorganosiloxane represented by the general formula (2).

(3)

[In general formula (1), X, R <^1> -R <^2> and a and b are the same as that of general formula (I), n represents the integer of 70-1000 as the average repeating unit number of organosiloxane structural unit. In the general formula ^{(2), R 3, R} 4, R 5 and R ⁶ each independently represents an alkyl or aryl group which may have a hydrogen atom or a substituent, Y is a halogen, -R ⁷ OH, -R ⁷ COOH , -R ⁷ NH ₂ , -COOH or SH, R ⁷ is a linear, branched or cyclic alkylidene group, an aryl substituted alkylidene group, an aryl substituted alkylene group or an aryl group which may have an alkoxy group on the ring; M represents 0 or 1;

Obtained by copolymerizing phosgene, carbonate ester, or chloroformate, the ratio of the polyorganosiloxane block portion containing the structural unit represented by General Formula (II) is 1 to 30% by mass, and the viscosity average molecular weight is 13000? Polycarbonate-polyorganosiloxane copolymer of 26000.

Moreover, in the polycarbonate resin composition of this invention, although there exist various things as bivalent phenol represented by General formula (1) used for the raw material of a polycarbonate polyorganosiloxane copolymer (A-1), Especially, , 2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is preferable.

Examples of bisphenols other than bisphenol A include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3- Methylphenyl) propane, bis (4-hydroxyphenyl) naphthyl methane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromo phenyl Propane, 2,2-bis (4-hydroxy-3,5-tetramethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy Bis (hydroxyaryl) alkanes, such as hydroxy-3, 5- dichlorophenyl) propane, 2, 2-bis (4-hydroxy-3, 5- dibromophenyl) propane, 1, 1-bis (4) -Hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcycle Bis (hydroxyaryl) cycloalkanes such as lohexane, 2,2-bis (4-hydroxyphenyl) norbornane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 4,4 ' Dihydroxy aryl ethers such as -dihydroxyphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4 ' Dihydroxy diaryl sulfides such as -dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 Dihydroxydiaryl sulfoxides such as' -dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Dihydroxy diphenyls, such as dihydroxy diaryl sulfones and 4,4'- dihydroxy diphenyl, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy) Dihydroxydiaryl fluorenes such as oxy-3-methylphenyl) fluorene , Bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane, 1,3-bis Dihydroxydiaryl adamantanes such as (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) -9-anthrone, 1,5-bis (4-hydroxyphenylthio) -2,3-dioxapentaene, etc. are mentioned.

These dihydric phenols may be used independently, respectively and may mix and use 2 or more types.

Illustrating the polyorganosiloxane represented by General formula (2), for example,

[Formula 4]

[In the general formulas (3) to (11), R ³ , R ⁴ , R ^5, and R ⁶ each independently represent a hydrogen atom, a halogen atom, or an alkyl group or an aryl group which may have a substituent. R ⁸ represents an alkyl, alkenyl, aryl or aralkyl group, n represents an integer of 70 to 1000 in terms of the average repeating unit number of the organosiloxane structural unit, and c represents a positive integer.]

And the like.

Among these, the phenol modified polyorganosiloxane shown in Formula (3) is preferable from the ease of superposition | polymerization, Furthermore, (alpha), omega-bis [3- (o-hydroxyphenyl) which is a kind in the compound shown in Formula (4) ), [Propyl] polydimethylsiloxane, or [alpha], omega-bis [3- (4-hydroxy-3- methoxyphenyl) propyl] polydimethylsiloxane which is a kind in the compound shown by Formula (5) is easy to obtain. Preferred at

The polyorganosiloxane represented by the general formula (2) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably a vinyl phenol, allyl phenol, eugenol, isopropenyl phenol, etc. It can be manufactured easily by hydrosilamination reaction to the terminal of a organosiloxane chain.

In the polycarbonate resin composition of the present invention, after the aromatic polycarbonate (A-2) other than (A-1) is reacted with a dihydric phenol compound and phosgene in the presence of an organic solvent and an aqueous alkali solution inert to the reaction, Or an interfacial polymerization method in which a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added to polymerize, or a dihydric phenol compound is dissolved in a mixed solution of pyridine or pyridine and an inert solvent, followed by direct introduction of phosgene. What is obtained by the conventional manufacturing method of aromatic polycarbonate, such as a pyridine method, is used.

At the time of the said reaction, a terminal terminator, a molecular weight regulator, a branching agent, etc. are used as needed.

As a dihydric phenol type compound used for manufacture of an aromatic polycarbonate (A-2), 2, 2-bis (4-hydroxyphenyl) propane [= bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) Phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) naphthyl methane, 1,1-bis ( 4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl Propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy Bis (hydroxyaryl) alkanes, such as oxy-3, 5- dibromophenyl) propane, 1, 1-bis (4-hydroxyphenyl) cyclopentane, 1, 1-bis (4- Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) norbornane, 1,1- Bis (hydroxyaryl) cycloalkanes such as bis (4-hydroxyphenyl) cyclododecane, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl Dihydroxy diaryl sulfides such as dihydroxyaryl ethers such as ether, 4,4'-dihydroxydiphenyl sulfide, and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide Dihydroxy diaryl sulfoxides, such as 4,4'- dihydroxy diphenyl sulfoxide, 4,4'- dihydroxy-3,3'- dimethyl diphenyl sulfoxide, 4,4'- Dihydroxy diaryl sulfones, such as dihydroxy diphenyl sulfone, 4,4'- dihydroxy-3,3'- dimethyl diphenyl sulfone, dihydroxy di, such as 4,4'- dihydroxy diphenyl Phenyls, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9- Dihydroxydiaryl fluorenes such as s (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) Dihydroxydiaryl adamantanes, such as carbon, 2,2-bis (4-hydroxyphenyl) adamantane, and 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane; , 4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) -9-anthrone, 1,5-bis (4-hydroxy Oxyphenylthio) -2,3-dioxapentaene etc. are mentioned.

These dihydric phenols may be used independently, respectively and may mix and use 2 or more types.

In the production of the aromatic polycarbonate (A-2), a terminal terminator or a molecular weight regulator is usually used.

As a molecular weight modifier, various things can be used as long as it is normally used for superposition | polymerization of polycarbonate resin.

Specifically, as monohydric phenol, it is phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot-, for example. Butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o- Cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol, m-nonylphenol, pn-nonylphenol, o-cumylphenol , m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5-di-t-butylphenol, 2,4-di-t-butylphenol , 3,5-di-t-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, p-cresol, bromophenol, tribromophenol, linear carbon atoms having an average carbon number of 12 to 35 Or monoalkylphenols having 9 or (4-hydroxyphenyl) -9- (4- with branched alkyl groups in ortho, meta or para positions; Ethoxyphenyl) fluorene, and the like of 9- (4-hydroxy-3-methylphenyl) -9- (4-methoxy-3-methylphenyl) fluorene, 4- (1-adamantyl) phenol.

Among these monohydric phenols, p-t-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferably used.

It is naturally possible to use 2 or more types of compounds together.

Further, the branching agent may be used in combination with 0.01 to 3 mol%, particularly 0.1 to 1.0 mol%, to the branched polycarbonate with respect to the divalent phenol compound, and as the branching agent, 1,1, 1-tris (4-hydroxyphenyl) ethane, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, α, α' , α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [α-methyl-α- (4'-hydroxyphenyl) ethyl] -4- [α ', The compound which has 3 or more functional groups, such as (alpha) '-bis (4 "-hydroxyphenyl) ethyl] benzene, a phlogroglycine, trimellitic acid, isatinbis (o-cresol), can be used.

Various additives known to the polycarbonate resin composition can be mix | blended conventionally with the polycarbonate resin composition used by this invention as needed, These include a reinforcing material, a filler, a stabilizer, antioxidant, a ultraviolet absorber, an antistatic agent. And lubricants, mold release agents, dyes, pigments, other flame retardants, and elastomers for improving impact resistance.

The polycarbonate resin composition used by this invention can be obtained by mix | blending and kneading said each component (A-1), (A-2), and well-known additives as needed.

The compounding and kneading | mixing are normally used for the method used, for example, a ribbon blinder, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a kneader, a multi screw extruder, etc. It can be carried out by.

In addition, the heating temperature at the time of kneading | mixing is normally selected in 250-320 degreeC.

In the molding of the obtained polycarbonate resin composition, various conventionally known molding methods, for example, injection molding method, injection compression molding method, extrusion molding method, blow molding method, press molding method, vacuum molding method and foam molding method can be used. It is preferable to carry out injection molding at 80 degreeC or more, Preferably it is 80-120 degreeC.

At this time, the resin temperature in injection molding is about 280-360 degreeC normally, Preferably it is 280-330 degreeC.

In addition, as the injection molding method, gas injection molding can be adopted to prevent the appearance of dents or to reduce the weight.

The thickness of the portable electronic device case obtained by molding the polycarbonate resin composition comprising the polycarbonate-polyorganosiloxane copolymer having the specific structure of the present invention is 0.5 to 1.5 mm, preferably 0.6 to 1.4 mm, more preferably Is 0.6-1.3 mm.

Moreover, although the portable electronic device case of this invention can be used for portable electronic devices, such as a portable PC, a portable information terminal (PDA), a mobile telephone, a portable player, and a battery case, a portable telephone is especially preferable.

Example

Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these examples.

[Production Example 1 of Polycarbonate-Polydimethylsiloxane Copolymer (PC / PDMS Copolymer)]

Polycarbonate Oligomer  Produce

To the bisphenol A (BPA) dissolved later in 5.6% by mass aqueous sodium hydroxide is added 2000 ppm of sodium dithionate, to which BPA is dissolved such that the BPA concentration is 13.5% by mass, and the aqueous sodium hydroxide solution of BPA is dissolved. It prepared.

At a flow rate of 40 liters / hr of sodium hydroxide aqueous solution of this BPA and 15 liters / hr of methylene chloride, phosgene was continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 4.0 kg / hr.

The tubular reactor had a jacket portion, and the cooling water was passed through the jacket to maintain the temperature of the reaction solution at 40 ° C or lower.

The reaction liquid exiting the tubular reactor was continuously introduced into a modeled reactor with a 40 liter baffle with a retracting wing, in addition to a 2.8 liter / hr, 25 mass% BPA aqueous sodium hydroxide solution. The reaction was performed by adding 0.07 liter / hr of sodium hydroxide aqueous solution, 17 liter / hr of water, and 0.64 liter / hr of 1 mass% triethylamine aqueous solution.

The reaction liquid overflowed from the tank reactor was continuously drawn out, and the water phase was separated and removed, and the methylene chloride phase was collected.

Thus, the obtained polycarbonate oligomer was 329 g / L in concentration and 0.74 mol / L in chloroformate group concentration.

Polycarbonate Polydimethylsiloxane  Preparation of Copolymer

Allylphenol terminal-modified polydimethylsiloxane having 15 L of polycarbonate oligomer solution, 9.0 L of methylene chloride, and 90 repeating units of dimethylsiloxane in a 50 L tank reactor equipped with a baffle plate, paddle stir blade and cooling jacket. (433 g of PDMS) and 8.8 mL of triethylamine were added thereto, 1389 g of a 6.4 mass% aqueous sodium hydroxide solution was added thereto under stirring, and the reaction of the polycarbonate oligomer and allylphenol terminal-modified PDMS was carried out for 10 minutes.

To this polymerization solution, a methylene chloride solution of pt-butylphenol (PTBP) (dissolved 126 g of PTBP in 2.0 L of methylene chloride) and an aqueous sodium hydroxide solution of BPA (NaOH 577 g and sodium dithionate 2.0 g, water 8.4 The solution which melt | dissolved B12 1012g in the aqueous solution melt | dissolved in L was added, and the polymerization reaction was performed for 50 minutes.

10 L of methylene chloride was added for dilution and stirred for 10 minutes, then separated into an organic phase comprising a polycarbonate-polydimethylsiloxane copolymer and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.

The methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer thus obtained was washed sequentially with the solution in 15 volume% of 0.03 mol / L NaOH aqueous solution and 0.2 mol / L hydrochloric acid, followed by electrical conductivity in the aqueous phase after washing. Washing was repeated with pure water until it became 0.01 μS / m or less.

The methylene chloride solution of the polycarbonate polydimethylsiloxane copolymer obtained by washing | cleaning was concentrated and pulverized, and the obtained flake was dried at 120 degreeC under reduced pressure.

PDMS residue amount (PDMS copolymerization amount) determined by nuclear magnetic resonance (NMR) of the obtained polycarbonate-polydimethylsiloxane copolymer was 5.6 mass%, the viscosity number measured based on ISO1628-4 (1999) was 51.2, viscosity average The molecular weight Mv was 19300.

[Production Examples 2 to 9 of Polycarbonate-Polydimethylsiloxane Copolymer (PC / PDMS Copolymer)]

The type of terminal-modified PDMS (allylphenol terminal-modified PDMS or eugenol terminal-modified PDMS), the number of repetitions of dimethylsiloxane units, the amount of terminal-modified PDMS, and the amount of PTBP used are as shown in Table 1, and polycarbonate-polydimethyl The siloxane copolymer was prepared.

Table 1 shows the PDMS residue amount (PDMS copolymerization amount), viscosity number, and viscosity average molecular weight Mv of the obtained polycarbonate-polydimethylsiloxane copolymer.

Examples 1-7 and Comparative Examples 1-3

Polycarbonate-polydimethylsiloxane copolymer (PC / PDMS copolymer) produced in Production Examples 1-9, FN1500 (trade name, manufactured by Idemitsu Heungsan Co., Ltd.), BPA polycarbonate having a pt-butylphenol as a terminal group, viscosity number 39.2, Viscosity Average Molecular Weight Mv = 14500), Teflon FN1700A (trade name, manufactured by Idemitsu Heungsan Co., Ltd., BPA polycarbonate having a pt-butylphenol as a terminal group, viscosity number 47.1, viscosity average molecular weight Mv = 17500), turfron Table 2 shows FN2700A (trade name, manufactured by Idemitsu Heungsan Co., Ltd.), BPA polycarbonate having pt-butylphenol as the terminal group, viscosity number 69.6, viscosity average molecular weight Mv = 27500), and IRGAFOS168 (trade name, manufactured by ADEKA Corporation) It blended like the mass part described, was granulated at the resin temperature of 280 degreeC using the 40 mm diameter single screw extruder with a vent, and the pellet was obtained.

In addition, only the comparative example 3 made resin temperature 300 degreeC.

After drying the obtained pellets at 120 degreeC for 8 hours, it injection-molded at the molding temperature of 280 degreeC, and die temperature of 80 degreeC using the injection molding machine, and obtained the test piece.

The following measurement was performed using the test piece obtained by pellet or injection molding.

The results are shown in Table 2.

(1) melt flowable MFR (melt flow rate)

In accordance with JIS K 7210, under a weight of 2.16 kg at 280 ° C, the amount of molten resin (g / 10 min) flowing out from the die having a diameter of 2 mm and a length of 8 mm was measured.

(2) Q value (flow value) [unit; 10 ^-2 ml / sec]

In accordance with JIS K 7210, an amount of molten resin (ml / sec) flowing out from a nozzle having a diameter of 1 mm and a length of 10 mm was measured under a pressure of 280 ° C. and 15.7 MPa using an elevated flow tester. .

The Q value represents the amount of outflow per unit time, and the higher the value, the better the fluidity.

(3) HDT (heat deformation temperature)

Based on ASTMD648, it measured by the load 0.45 MPa.

HDT represents the standard of heat resistance.

[Molding of cell-phone model type]

The molded article (50 mm x 88 mm, depth 4.5 mm, thickness 1.2 mm) shown in the dimension explanatory drawing of FIG. 1 was obtained by injection molding on the following conditions using the pellet obtained above.

Moreover, although injection molding was attempted about the comparative example 3, the viscosity was high at the cylinder temperature of 300-320 degreeC, filling was impossible, and the molded article was not obtained.

Moreover, although shaping | molding was attempted by raising cylinder temperature to 360 degreeC, the molded article could not be obtained, but as a result of coloring by the deterioration of a resin composition as a result of raising cylinder temperature to 380 degreeC, shaping | molding was stopped.

Molding conditions

Injection molding machine: 80 tons of electric injection molding machine ES-1000 manufactured by Nissei Resin Industry Co., Ltd.

Molding Machine Cylinder Temperature: 300? 320 ℃

Molding cycle: 30 seconds / cycle

Mold temperature: 130 ℃

[Falling impact resistance evaluation]

The obtained molded article was put into a thermostat and cooled to predetermined temperature (0 degreeC, -10 degreeC, -20 degreeC).

After 2 hours, the molded product was taken out of the thermostat and the drop impact resistance was evaluated by immediately dropping a weight of 1280 g into the molded product at a height of 1.85 m.

The same test was carried out five times, and the presence or absence of cracks, the occurrence of cracks, and the kind of cracks (ductile cracks and brittle cracks) are shown in Table 2.

The case where the cracked surface (breaking surface) was soft was evaluated as the case where the soft crack and the cracked surface were brittle as a brittle crack.

In addition, a numerical value shows the presence or absence of a crack in five tests, the presence or absence of a crack, and the frequency | count of the kind of a crack, and the sum totals five.

Industrial availability

According to the present invention, it is possible to provide a portable electronic device case which is thin and excellent in dropping impact resistance, fluidity and heat resistance.

Claims (4)

Content of the polyorganosiloxane block part which has a structural unit represented by general formula (I) and the structural unit represented by general formula (II), and contains the structural unit represented by general formula (II) is 1-30 mass%, In addition, 10-100 mass parts of polycarbonate-polyorganosiloxane copolymer (A-1) whose average repeating unit number of the structural unit of the general formula (II) is 70-1000, and a viscosity average molecular weight is 13000-26000, and A portable electronic device case comprising a polycarbonate resin composition containing 0 to 90 parts by mass of an aromatic polycarbonate (A-2) other than (A-1) such that the total amount is 100 parts by mass.
[Formula 1]

[In formula, R <^1> and R <^2> is respectively independently a C1-C6 alkyl group or an alkoxy group, X is a single bond, a C1-C8 alkylene group, a C2-C8 alkylidene group, and a C5-C15 The cycloalkylene group, the cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO _2- , -O- or -CO-, R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom or An alkyl group or an aryl group which may have a substituent, and a and b each independently represent an integer of 0 to 4; The method of claim 1,
A portable electronic device case molded by injection molding. The method of claim 2,
A portable electronic device case having a thickness of 0.5 to 1.5 mm of the portable electronic device case. The method according to claim 2 or 3,
A portable electronic device case in which the portable electronic device of the portable electronic device case is a mobile phone.