TWI546332B - A polycarbonate resin composition, and a molded product composed of the resin composition - Google Patents

Description

Polycarbonate resin composition and molded article composed of the resin composition Technical field

The present invention relates to a polycarbonate resin composition and a molded article comprising the resin composition, and more particularly to the fact that the resin composition does not yellow or silver streaks during high-temperature molding, and the release property is obtained. A polycarbonate resin composition which is excellent in adhesion to a mold and a molded article composed of the resin composition.

Background technique

In recent years, the thinning of liquid crystal displays has continued to progress, and an injection-molded light guide plate having a thickness of 0.25 mm has been successfully developed. However, the fluidity of the polycarbonate is insufficient, and it is extremely difficult to form a thin light guide plate, and it is often the case that the polycarbonate is not formed at 280 ° C to 320 ° C under the general recommended molding conditions. For this reason, there are cases in which it is formed at a temperature of 360 ° C to 380 ° C which is not the usual condition, but there is a streak which is called a silver streak entering the surface of the molded article, or the polycarbonate turns yellow, so that the backlight unit is The generated light has a yellow sensation, and the transmittance is lowered. Even if it is formed as a light guide plate, it does not function.

For example, there is a proposal for a resin composition for a light guide plate, that is, an antioxidant and a release agent are added by a polycarbonate resin having a molecular weight of 13,000 to 15,000, and the light transmittance, thermal stability, and formability are excellent (patent Document 1). Further, there is a proposal of a resin composition in which an organopolysiloxane is added to a polycarbonate resin, the organopolyoxane having a phenyl group at least in a side chain and having a branched oxime structure at 25 ° C The dynamic viscosity is 1 to 200 cSt, whereby the generation of gas can be suppressed, and the color tone is excellent (Patent Document 2).

However, when the antioxidant resin and the release agent are added to the polycarbonate resin disclosed in Patent Document 1, the following problems are derived: that, under the molding conditions of 360 ° C or higher, a majority which is regarded as a poor appearance is produced. Silver streaks, for example, do not function as a function of the light guide plate. Further, as disclosed in Patent Document 1, when the content of the low molecular weight aromatic polycarbonate polymer having a molecular weight of less than 1,000 is 2% by mass or less, mold adhesion or appearance deterioration can be suppressed, but the formation of a light guide plate and CD Or the formation of a disc such as a DVD is different, and there are many types of forming conditions or methods for the light guide plate. When focusing on a component having a molecular weight of 1000 or less, there is a problem that the mold cannot be prevented from being attached.

Further, in the resin composition of Patent Document 2, there is a problem in that the gas generation in the high-temperature molding conditions of 340 ° C or higher and the mold adhesion are still insufficient.

In addition, when silver streaks are formed on the molded article, it cannot be shipped as a product, and when the mold is attached, there is a mark of adhesion on the molded article. Therefore, in addition to being not able to be shipped as a product, it is necessary to The problem of shutting down the forming machine is derived from cleaning. In particular, since the light guide plate mold has fine flaws, lenses, and the like, there is a risk of injuring the fine structure when the number of times of cleaning is increased, and therefore it is necessary to avoid it.

Advanced technical literature [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2007-204737

[Patent Document 2] Japanese Patent Application Publication No. 2005-96421

The present invention has been made to solve the above problems caused by a polycarbonate resin composition, and an object thereof is to provide a polycarbonate resin composition and a molded article comprising the resin composition, which reduces the aforementioned The resin composition is yellow, the generation of silver streaks, the adhesion of a mold, and the like, and the release property is excellent.

In order to achieve the above object, the present inventors have carefully reviewed and studied the components and additives of the polycarbonate resin composition, and as a result, found a polycarbonate resin composition which can achieve the above object. The present invention has been completed based on the above findings.

That is, the present invention is intended to be the following.

A polycarbonate resin composition comprising: 0.01 to 0.15 parts by mass of a phosphite represented by the following general formula (I) and/or (II) with respect to 100 parts by mass of the polycarbonate; , methoxy and vinyl organic polyoxane compounds 0.01 to 0.15 parts by mass;

[Chemical 1]

Wherein R ¹ represents an aryl group or an alkyl group, and may be the same or different;

[Chemical 2]

In the formula (II), R ⁹ is an alkyl group having 1 to 20 carbon atoms, and R ¹⁰ to R ¹⁴ are a hydrogen atom, an aryl group or an alkyl group having 1 to 20 carbon atoms, and each group may be the same or different.

2. The polycarbonate resin composition according to the above item 1, wherein the content of the phosphite and the organopolyoxane compound is 0.03 to 0.1 part by mass.

3. The polycarbonate resin composition according to Item 1 or 2 above, wherein the acetone-soluble portion of the polycarbonate is 9% by mass or less.

A molded article obtained by molding the polycarbonate resin composition according to any one of items 1 to 3 above.

A light guide plate, a film or a sheet which is formed by molding the polycarbonate resin composition according to any one of items 1 to 3 above.

The present invention provides a polycarbonate resin composition and a molded article comprising the resin composition, which can reduce yellowing of a polycarbonate resin composition, generation of a silver streak, adhesion of a mold, and the like, and is excellent in release property. By.

Embodiment of the present invention

Hereinafter, the present invention will be described in detail.

The present invention is a polycarbonate resin composition containing 0.01 to 0.15 parts by mass of the phosphite represented by the following general formula (I) and/or (II) with respect to 100 parts by mass of the polycarbonate; , an organic polyoxyalkylene compound having a phenyl group, a methoxy group and a vinyl group, 0.01 to 0.15 parts by mass,

[Chemical 3]

In the formula (I), R ¹ represents an aryl group or an alkyl group, and may be the same or different;

[Chemical 4]

In the formula (II), R ⁹ is an alkyl group having 1 to 20 carbon atoms, and R ¹⁰ to R ¹⁴ are a hydrogen atom, an aryl group or an alkyl group having 1 to 20 carbon atoms, and each group may be the same or different.

Among the phosphites represented by the formula (I) and/or (II), the phosphite represented by the formula (I) is particularly preferred.

In the present invention, the polycarbonate and the phosphite represented by the above formula (I) and/or (II) and the organopolyoxane compound having a phenyl group, a methoxy group and a vinyl group are respectively compounded. A predetermined amount of the polycarbonate resin composition can provide a significant double multiplication effect that can solve the problem of the present invention.

The polycarbonate resin to be used in the present invention is not particularly limited, and those produced by various methods known to date can be used. For example, a dihydric phenol and a carbonate precursor are used in the presence of a solution by a solution method (interfacial polycondensation method) or by a melt method (transesterification method), that is, a terminal phenol and a terminal phenol. Manufactured by a transesterification method of phosgene (carbon chloro; phosgene) reaction or a terminal eliminator by a transesterification method such as dihydric phenol and diphenyl carbonate.

As the dihydric phenol, various dihydric phenols can be exemplified, and in particular, 2,2-bis(4-hydroxyphenyl)propane [general name: bisphenol A] is suitable. For bisphenols other than bisphenol A, for example, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl) butyl Alkane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-1-methylphenyl) Propane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxy-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane , 2,2-bis(4-hydroxy-3,5-tetramethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxyl a bis(hydroxyaryl)alkane such as -3,5-tetrachlorophenyl)propane or 2,2-bis(4-hydroxy-3,5-tetrabromophenyl)propane; 1,1-double ( 4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane a bis(hydroxyaryl)cycloalkane such as an alkane; a dihydroxy aryl ether such as 4,4'-dihydroxyphenyl ether or 4,4'-dihydroxy-3,3'-dimethylphenyl ether; , 4'-dihydroxydiphenyl sulfide; 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide Dihydroxydiaryl sulfides; dihydroxydiaryl groups such as 4,4'-dihydroxydiphenylarylene, 4,4'-dihydroxy-3,3'-dimethyldiphenylarylene Anthraquinone; dihydroxydiaryl fluorene such as 4,4'-dihydroxydiphenyl hydrazine, 4,4'-dihydroxy-3,3'-dimethyldiphenyl hydrazine; 4,4'-di Dihydroxybenzenes such as hydroxydiphenyl. These dihydric phenols may be used alone or in combination of two or more.

On the other hand, in the case of a carbonate precursor, such as a carbonium halogen, a carbonyl ester or a haloformate, specifically, phosgene (carbonium chloride), a dihaloformate of a dihydric phenol, and a carbonic acid Phenyl ester, dimethyl carbonate and diethyl carbonate.

Further, this general PC resin may have a branched structure, and in the case of a branching agent, there are 1,1,1-tris(4-hydroxyphenyl)ethane, α,α',α"-tris(4-hydroxybenzene). Base)-1,3,5-triisopropylbenzene, fluorinated glycine, trimellitic acid, and 1,3-bis(o-cresol).

In the case of the aforementioned terminal stopper, a monovalent carboxylic acid and a derivative thereof and a monovalent phenol can be used. For example, p-tert-butyl-phenol, p-phenylphenol, p-cumenylphenol, p-perfluorononylphenol, p-(perfluorodecylphenyl)phenol, p-(perfluorooxybenzene) Phenyl, p-tert-perfluorobutylphenol, 1-(p-hydroxybenzyl)perfluorodecane, p-[2-(1H,1H-perfluorotridodecyloxy)-1,1,1 ,3,3,3-hexafluoropropyl]phenol, 3,5-bis(perfluorohexyloxycarbonyl)phenol, perfluorododecyl p-hydroxybenzoate, p-(1H,1H-perfluorooctyloxy Phenol, 2H, 2H, 9H-perfluorodecanoic acid, 1,1,1,3,3,3-tetrafluoro-2-propanol and the like.

In addition, it may also contain a branching agent, for example, 1,1,1-tris(4-hydroxyphenyl)ethane; α,α',α"-tris(4-hydroxyphenyl)-1,3, 5-triisopropylbenzene; a compound having three or more functional groups such as fluorinated glycine, trimellitic acid, and 1,3-bis(o-cresol).

In the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin is usually 10,000 to 50,000, preferably 13,000 to 35,000, more preferably 14,000 to 20,000.

The viscosity average molecular weight (Mv) is determined by measuring the viscosity of the methylene chloride solvent at 20 ° C using a Uber Lauder type viscometer, thereby obtaining the ultimate viscosity [η], which is calculated by the following formula:

[η] = 1.23 × 10 ^-5 Mv ^0.83 .

Next, in the present invention, a phosphite is used. The phosphite may be exemplified by the formula (I) and/or the formula (II), and the like, and particularly preferably the formula (I).

【化5】

In the formula (I), R ¹ represents an aryl group or an alkyl group, and may be the same or different.

In the general formula (I), R ¹ is an aryl group, R ¹ Department of the following general formula (a), (b), or formula (c) shown in the preferred aryl group.

【化6】

In the formula (a), R ² represents an alkyl group having 1 to 10 carbon atoms.

【化7】

In the formula (b), R ³ represents an alkyl group having 1 to 10 carbon atoms.

【化8】

In the case of the phosphite represented by the formula (I), in the present invention, a commercially available product, Adcaster PEP36 (trade name; manufactured by Nissho Asahi Chemical Co., Ltd.) can be used, but not Only limited to PEP36.

【化9】

In the formula (II), R ⁹ is an alkyl group having 1 to 20 carbon atoms, and R ¹⁰ to R ¹⁴ are a hydrogen atom, an aryl group or an alkyl group having 1 to 20 carbon atoms, and each group may be the same or different.

In the present invention, a commercially available product of Adcaster cloth C (trade name; manufactured by Nissho Asahi Chemical Co., Ltd.) can be used, but it is not limited to the case of the phosphite represented by the formula (II). Adecaster C.

The phosphite represented by the formula (I) and/or (II) is added in an amount of 0.01 to 0.15 parts by mass, preferably 0.03 to 0.1 parts by mass, more preferably 100 parts by mass, based on 100 parts by mass of the polycarbonate. 0.03 to 0.07 parts by mass.

When the addition amount of the phosphite represented by the general formulae (I) and /(II) is in the range of 0.01 to 0.15 parts by mass based on 100 parts by mass of the polycarbonate, the synergistic effect is exhibited in combination with other components, except for oxidation resistance. In addition to the effect, even under the molding conditions of a high temperature of 340 ° C or higher, the effect of greatly reducing the occurrence of gas, yellowing, and mold adhesion can be exhibited.

On the other hand, when the amount is less than 0.01 parts by mass, a sufficient effect cannot be exhibited, and when it exceeds 0.15 parts by mass, the adhesion of the mold is increased, and the heat resistance of the resin composition is lowered.

On the other hand, the organopolyoxyalkylene compound is essential for having a phenyl group, a methoxy group, and a vinyl group, and the lack of either one cannot achieve the desired effect. For example, the use of methylphenyl siloxane or the like is disclosed in Japanese Laid-Open Patent Publication No. 2004-250557, but the organic polyoxy siloxane compound of the present invention is structurally different from the compound.

The organopolyoxane compound may be a phenyl group, a methoxy group or a vinyl group, and it is preferred to use a dynamic viscosity at 25 ° C of from 1 to 500 cSt.

The organopolysiloxane compound having a phenyl group, a methoxy group and a vinyl group is added in an amount of 0.01 to 0.15 parts by mass, preferably 0.03 to 0.1 parts by mass, more preferably 100 parts by mass of the polycarbonate, more preferably Add 0.03 to 0.07 parts by mass.

When the amount of addition is in the range of 0.01 to 0.15 parts by mass based on 100 parts by mass of the polycarbonate, the effect can be exhibited in synergy with other components, in addition to the effect of improving the release property, and even at a temperature higher than 340 ° C or higher. The molding conditions, especially under continuous molding conditions, can also exhibit the effect of greatly reducing the occurrence of silver streaks and mold adhesion.

On the other hand, when the amount is less than 0.01 parts by mass, a sufficient effect cannot be exhibited, and when it is added in an amount of more than 0.15 parts by mass, there is a risk that the adhesion of the mold is increased or the resin becomes cloudy.

In the present invention, KR-511 (manufactured by Nissho Shin-Etsu Chemical Co., Ltd.; trade name) of a commercially available product can be used as the organic polysiloxane compound having a phenyl group, a methoxy group and a vinyl group, but it is not limited only. For KR-511.

The polycarbonate resin composition of the present invention obtains the following polycarbonate resin composition by containing the above components, that is, in the high-temperature molding conditions, the molded article can be yellowed or silver streaks and mold adhesion can be produced. In the case where the acetone-soluble portion of the polycarbonate used in the present invention is adjusted to 9 mass% or less, the adhesion of the mold can be further suppressed, which is preferable.

In other words, when the low-molecular component which is easily decomposed by the reason why the mold is adhered at the time of high-temperature molding is examined, it is known that the low-molecular component having a molecular weight of less than 1,000 is only 2% by mass. In the following, in the high-temperature molding, the adhesion of the mold cannot be prevented.

Here, in the present invention, the low molecular component in the polycarbonate which is easily decomposed during molding is focused on a molecular weight of 5,000 or less. In the detection method of the component having a molecular weight of 5,000 or less, an acetone-soluble portion is used. In other words, in the present invention, it is found that when the oligomer is synthesized, the polymerization ratio of the catalyst, the terminal stopper, etc., the optimization of the timing of the introduction, and the purification step of the solvent are found during the polymerization of the polymer. When the acetone-soluble portion is 9% by mass or less, the adherer of the mold can be more significantly suppressed.

When the acetone-soluble portion of the polycarbonate is made 9% by mass or less, it is possible to prevent the adhesion of the mold even in the molding of the light guide plate having various molding conditions or molding methods.

The method for producing the polycarbonate resin composition of the present invention is not particularly limited. The polycarbonate is mixed with the above components and melt-kneaded. Melt-kneading can be carried out by a commonly used method, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum mill, a single-axis screw extruder, a biaxial spiral It is carried out by a method such as an extruder, a kneading extruder (ko-kneader), a multi-axis screw extruder, or the like. The heating temperature at the time of melt-kneading can be appropriately selected within the range of 220 to 280 °C.

An example of a specific manufacturing method is given below.

In other words, first, 0.01 to 0.15 parts by mass of an organopolysiloxane compound having a phenyl group, a methoxy group, and a vinyl group is added to 100 parts by mass of the polycarbonate, and a ribbon blender or a Banbury mixture is used. After sufficiently mixing with a known mixer such as a machine, a drum type tumbling machine, a Henschel mixer, or a floater, 0.01 to 0.15 parts by mass of the phosphite represented by the above formula (1) is further added, and the above mixer is again used. Mix thoroughly. The mixture thus obtained is heated to a cylinder temperature of 240 to 280 ° C for melting using a single-axis screw extruder, a twin-screw extruder, a kneading extruder, a multi-axis screw extruder, and the like. Mixing. Thereafter, when the granules are granulated using a granulator or the like, the polycarbonate resin composition of the present invention can be obtained.

Further, the phosphite represented by the above formula (1) and/or (II) and the organopolyoxyalkylene compound having a phenyl group, a methoxy group and a vinyl group may be simultaneously added to the polycarbonate to be mixed.

In the polycarbonate resin composition of the present invention, the melt-kneaded product or the obtained resin pellet is used as a raw material, and a known molding method such as a hollow molding method, an injection molding method, an injection compression molding method, or an extrusion molding method is used. Forming method such as vacuum forming method, blow molding method, press forming method, pressure forming method, foam molding method, hot bending method, compression molding method, calender molding method, and rotary molding method can form transparency Excellent molded product.

In the present invention, a light guide plate, a lens, and a film can be exemplified for such a molded article.

Among them, the light guide plate is not particularly limited as long as it is formed into a flat plate having a thickness of about 3 mm. Further, the shape is not necessarily limited to a flat plate shape, and may be a curved panel having a lens effect, and may be appropriately selected depending on the purpose and use. For example, the thickness of the light guide plate may be a structure in which a wedge-shaped cross section which is formed to be thinner away from the light source may be formed. Further, a structure in which a display portion composed of another member is integrally provided on the front surface of the planar light-emitting body may be employed.

In order to obtain uniform planar light emission, it is necessary to form a light scattering layer which is deeper toward the back surface of the light guide plate when it is farther away from the light source. For this purpose, printing treatment may be applied to any of the surface or the back surface of the formed plate. That is, a white paint having a reflective property is usually used to form a dense pattern such as a dot or a slit. Further, in addition to dot printing, a method of simultaneously forming a prismatic cut at the time of injection molding at the time of fabricating a light guide plate, that is, a method of prismatic transfer can be employed.

Further, when the light guide plate forms such a light scattering layer, it is not limited to the entire light guide plate, and may be formed in a part.

In the light guide plate, the lens or the film which is a molded article of the present invention, it is possible to provide a product which is capable of suppressing yellowing, silver streaks, and the like which are easily generated at the time of high-temperature molding, and which is excellent in transparency. Further, since a molded article containing a polycarbonate resin which is excellent in mold adhesion and excellent in release property can be obtained, the molding efficiency can be extremely improved.

In the present invention, in addition to the above components, various additives may be blended to the extent that the properties are not impaired. The additive may be a light stabilizer such as an interference phenol type, an aryl phosphine type or an ester type other than the phosphite, a light diffusing agent, an ultraviolet absorber, or an interference type amine. Examples of fuels, flame retardant aids, colorants, antistatic agents, anti-caking agents, weathering agents (anti-aging agents), release agents other than the above-mentioned organic polyoxoxanes, plasticizers and lubricants .

Among them, for the aforementioned antioxidant, the following compounds can be exemplified, for example, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, tridecyl phosphite , tridecyl phosphite, tricresyl phosphite, trialkyl phosphite such as pentaerythritol diphosphite distearate; tricycloalkyl phosphite such as tricyclohexyl phosphite; a triphenyl phosphite such as phenyl, tricresyl phosphite, tris(ethylphenyl) phosphite, tris(butylphenyl) phosphite, or 2-ethylhexyl diphenyl phosphite a monoalkyl diaryl phosphate; a trialkyl phosphate such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, or octadecyl phosphate; tricyclohexyl phosphate Tricycloalkyl phosphate such as ester; triaryl phosphate such as triphenyl phosphate or tricresyl phosphate; triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris-(p-toluene) An arylphosphine such as a phosphine, a tris-(p-nonylphenyl)phosphine, a tris-(naphthyl)phosphine or the like.

In addition, commercially available products of interfering phenol-based antioxidants include "Illrox 1076" (trade name; Girard-Perregaux) and "Irrox 1010" ( Product name; Girard-German company), "ethyl 330" (trade name; American company Aiqier (transliteration) company), "Sumi Lai (transliteration) GM" (trade name; Nissho Sumitomo Chemical Co., Ltd. System) as an example.

Further, as the light diffusing agent, the following particles may be exemplified, such as: crosslinked polymethacrylate resin particle resin particles, siloxane oxide resin particles, cerium oxide particles, quartz particles, and dioxide. Any one of 矽 繊 繊, quartz fiber quartz 繊 and glass fiber, or a combination of two or more.

Further, the ultraviolet absorber is preferably a compound selected from the group consisting of a malonate compound, a grassy alanine compound, and a benzotriazole compound. These compounds may be used alone or in combination of two or more.

The malonic ester-based compound may, for example, be benzylidenebisdiethylmalonate or 4-methoxyphenyl-methylene-dimethylester. The grasshopper-like alanine-based compound is exemplified by a grasshopper-alanine-based compound having a hydrocarbon number of 1 to 12 carbon atoms. The benzotriazole-based compound is preferably an acrylate-based polymer having a side chain of a benzotriazole-based skeleton.

The present invention will be described below by way of examples and comparative examples of the invention, but the invention is not limited thereto.

real Example [Examples 1 to 8 and Comparative Examples 1 to 8]

The components were mixed at a ratio shown in Table 1, and then kneaded by a uniaxial kneading extruder (caliber: 40 mm ,), and kneaded at 280 ° C, a screw rotation number of 100 rpm, and a discharge amount of 15 kg / hr. grain. In addition, in Table 1, the data showing the addition ratio of each component shows the mass part with respect to 100 mass parts of polycarbonate resin.

Next, the particles obtained in the above steps were dried by hot air at 120 ° C for 5 hours, and then a molding machine (manufactured by Nissan Sumitomo Heavy Industries Co., Ltd.; Sumitomo Nesta/N515/150) was used at 380 ° C. At the molding temperature and the mold temperature of 80 ° C, the molding cycle was constant, and the residence time in the cylinder was constant, and after the 20 shot molding, the sputum sampling was started. By the adjustment of the cooling time, a total light transmittance, a yellowness (YI), and a flat panel for appearance evaluation of 40 mm × 80 mm × 3.0 mm in the molding machine for 5 minutes and 20 minutes were prepared.

For the samples obtained by injection molding, the total light transmittance and the yellowness were measured by a test machine manufactured by Nippon Denshoku Industries Co., Ltd., based on JIS K7105.

In addition, the appearance of the sample in the obtained molding machine for 20 minutes was visually observed (whether or not silver streaks were generated), and the evaluation was performed based on the following evaluation criteria.

◎‧‧No silver streaks were observed.

○‧‧ Some silver streaks were observed, but the types of products may be allowed.

×‧‧After seeing a lot of silver streaks, it has not been allowed as a product.

××‧‧ It was observed that there were a lot of silver streaks, which had reached an unacceptable level as a product.

Furthermore, the obtained pellets were each dried at 120 ° C for 5 hours in hot air, and then 1500 shots were continuously formed at a molding temperature of 340 ° C and a mold temperature of 80 ° C using SG100M-HP manufactured by Sumitomo Heavy Industries, Ltd., to obtain 40 mm × Sample of 80mm × 2.0mm. After 1500 shot continuous molding, the mold internal mold was taken out, and the mold adhesion was visually observed, and the evaluation was performed based on the following evaluation criteria.

◎‧‧No attachments were observed.

○‧‧ Some attachments were observed.

×‧‧A lot of attachments were observed.

××‧‧A lot of attachments were observed.

In addition, the types of materials used in the present examples and comparative examples are described below.

(A) polycarbonate

‧PC-1: Made by Nissho Idemitsu Kosan Co., Ltd.; bisphenol A polycarbonate; viscosity average molecular weight 15000; acetone soluble part: 8.5% by mass

‧PC-2: Made by Nissho Idemitsu Co., Ltd.; bisphenol A polycarbonate; viscosity average molecular weight 14000; acetone soluble part: 8.7% by mass

‧PC-3: Made by Nissho Idemitsu Co., Ltd.; bisphenol A polycarbonate; viscosity average molecular weight 17000; acetone soluble part: 8.5% by mass

‧PC-4: Made by Nissho Idemitsu Co., Ltd.; bisphenol A polycarbonate; viscosity average molecular weight 15000; acetone soluble part: 11.7% by mass

‧PC-5: Made by Nissho Idemitsu Co., Ltd.; bisphenol A polycarbonate; viscosity average molecular weight 17000; acetone soluble part: 10.1% by mass

Further, in the above, the method for measuring the acetone soluble portion is as follows.

Using an acetone solvent, 20 g of the sample was extracted at 80 ° C for 3 hours, and then filtered, dried and solidified using an evaporator, and then the acetone extraction amount was calculated.

The method for producing the above polycarbonate PC-1 to PC-5 is as follows.

Production Example 1 (manufacture of polycarbonate PC-1) (1) Polycarbonate oligomer synthesis step

To a 5.6 mass% aqueous sodium hydroxide solution, sodium dithionite (Na ₂ S ₂ O ₄ ) was added in an amount of 0.2% by mass based on bisphenol A (BPA) which was dissolved later, and BPA was dissolved therein to form a BPA concentration of 13.5. 5% by mass, and a sodium hydroxide aqueous solution of BPA was prepared. In a tubular reactor having an inner diameter of 6 mm and a length of 30 m, the above aqueous solution of BPA sodium hydroxide was flowed at a flow rate of 40 L/hr, and dichloromethane was continuously introduced therein at a flow rate of 15 L/hr, and phosgene (carbon enthalpy) was introduced. Chlorine) was introduced at a flow rate of 4.0 kg/hr. The tubular reactor has a jacket portion through which cooling water is passed to maintain the temperature of the reaction liquid below 40 °C. The reaction liquid sent from the tubular reactor is continuously introduced into a tank type reactor having a backing blade and having an inner volume of 40 L, and a baffle-type reactor is further supplied with a sodium hydroxide aqueous solution of BPA at a flow rate of 2.8 L/hr. A flow rate of 0.07 L/hr was supplied to a 25 mass% sodium hydroxide aqueous solution, and water was supplied at a flow rate of 17 L/hr, and a 1 mass% triethylamine aqueous solution was supplied at a flow rate of 0.64 L/hr, and the reaction was carried out at 29 ° C to 32 ° C. The reaction liquid was continuously withdrawn from the tank type reactor, and the aqueous phase was separated and removed by standing, and a dichloromethane phase was collected. The polycarbonate oligomer solution thus obtained had an oligomer concentration of 338 g/L and a chloroformic acid group concentration of 0.71 mol/L.

(2) Polycarbonate polymerization step

Into a trough reactor having a buffer plate and a paddle type stirring blade and having an internal volume of 50 L, 15.0 L of the above oligomer solution, 10.0 L of dichloromethane, 182 g of p-tert-butylphenol (PTBP), and triethyl acetate were placed. 1.5 mL of an amine, here, a sodium hydroxide aqueous solution of bisphenol A (BPA) was added (in a solution of 1.1 kg of bisphenol A (BPA) dissolved in an aqueous solution of 642 g of sodium hydroxide and 2.2 g of sodium dithionite. The polymerization reaction was carried out for 1 hour by dissolving in 9.4 L of water. After diluting and adding 10.0 L of dichloromethane, the mixture was allowed to stand still, and the organic phase containing polycarbonate was separated from the aqueous phase containing excess bisphenol A (BPA) and sodium hydroxide, and the organic phase was separated.

(3) Washing step

The dichloromethane solution of the polycarbonate obtained in the above step (2) is sequentially washed with a 0.03 mol/L sodium hydroxide aqueous solution and 0.2 mol/L hydrochloric acid in an amount of 15% by volume with respect to the solution thereof, followed by washing, followed by The mixture is washed repeatedly with pure water until the conductivity in the aqueous phase after washing is 0.05 μS/m or less.

(4) Thinning step

The polycarbonate solution of the polycarbonate obtained in the above step (3) was concentrated and pulverized to obtain a polycarbonate flake (PC-1). The obtained sheet was dried at 120 ° C for 12 hours under reduced pressure. The polycarbonate obtained had a viscosity average molecular weight of 15,000 and an acetone soluble fraction of 8.5%.

Production Example 2 (manufacture of polycarbonate PC-2)

The (2) third butyl phenol (PTBP) in the polycarbonate polymerization step was changed to 199 g, and the rest was carried out in the same manner as in the production of PC-1. The viscosity average molecular weight was 14,000, and the acetone soluble fraction was 8.7%.

Production Example 3 (manufacture of polycarbonate PC-3)

The same procedure as in the production of PC-1 was carried out except that the p-tert-butylphenol (PTBP) in the (3) polycarbonate polymerization step was changed to 154 g. The viscosity average molecular weight was 17,000 and the acetone soluble fraction was 8.5%.

Production Example 4 (manufacture of polycarbonate PC-4) (1) Polycarbonate oligomer synthesis step

To a 5.6 mass% aqueous sodium hydroxide solution, sodium dithionite (Na ₂ S ₂ O ₄ ) was added in an amount of 0.2% by mass based on bisphenol A (BPA) which was dissolved later, and BPA was dissolved therein to form a BPA concentration of 13.5. % by mass, a sodium hydroxide aqueous solution of BPA was prepared. In a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m, the aqueous solution of sodium hydroxide of BPA was flowed at a flow rate of 40 L/hr, and dichloromethane was continuously introduced therein at a flow rate of 15 L/hr, and was 4.0 kg/ The flow of hr continuously enters phosgene (carbon ruthenium chloride). The tubular reactor has a jacket portion through which cooling water is passed to maintain the temperature of the reaction liquid below 40 °C. The reaction liquid sent from the tubular reactor was continuously withdrawn, and the aqueous phase was separated and removed in a standing manner to collect a dichloromethane phase. The polycarbonate oligomer solution thus obtained had an oligomer concentration of 280 g/L and a chloroformic acid group concentration of 1.02 mol/L.

(2) Polycarbonate polymerization step

Into a trough reactor having a buffer plate and a paddle type stirring blade and having an internal volume of 50 L, 12.5 L of the above oligomer solution, 10.8 L of methylene chloride, 166 g of p-tert-butylphenol (PTBP), and triethyl benzoate were placed. 1.8 mL of an amine, here, a sodium hydroxide aqueous solution of bisphenol A (BPA) was added (in a solution of 1.3 kg of bisphenol A (BPA) dissolved in an aqueous solution of 765 g of sodium hydroxide and 2.7 g of sodium dithionite. The polymer was dissolved in 11.2 L of water to carry out a polymerization reaction for 1 hour. For the purpose of dilution, after adding 10.0 L of dichloromethane, the mixture was allowed to stand, and the organic phase containing polycarbonate was separated from the aqueous phase containing excess bisphenol A (BPA) and sodium hydroxide, and the organic phase was separated.

(3) Washing step

The dichloromethane solution of the polycarbonate obtained in the above step (2) is washed in the order of 15% by volume of a 0.03 mol/L sodium hydroxide aqueous solution and 0.2 mol/L hydrochloric acid with respect to the solution, followed by The pure water is repeatedly washed until the conductivity in the aqueous phase after washing is 0.05 μS/m or less.

(4) Thinning step

The dichloromethane solution of the polycarbonate obtained in the above step (3) was concentrated and pulverized to obtain a polycarbonate flake (PC-4). The obtained sheet was dried at 120 ° C for 12 hours under reduced pressure. The polycarbonate obtained had a viscosity average molecular weight of 15,000 and an acetone soluble fraction of 11.7%.

Production Example 5 (manufacture of polycarbonate PC-5)

(2) The same procedure as in the production of PC-4 was carried out except that the PTBP of the polymerization step of the polycarbonate was changed to 141 g. The viscosity average molecular weight was 17,000, and the acetone soluble fraction was 10.1%.

(B) Antioxidants

‧Antioxidant-1: Adcaster cloth PEP36 [commodity name; bismuth (2,6-di-t-butyl-4-methylphenyl) ester of pentaerythritol diphosphite) ]

‧Antioxidant-2: Irg (Ilgarfoss) 168 [trade name; Girard-Perregaux Chemical Co., Ltd.; Tris(2,4-di-t-butylphenyl) phosphite]

‧Antioxidant-3: Irg (Ilgarfoss) 38 [trade name; Girard-Perregaux Specialty Chemicals; bis(2,4-t-butyl-6-methylphenyl)ethyl-phosphite]

‧Antioxidant-4: Ilgafoss P-EPQ [trade name; Girard-Perregaux Specialty Chemicals Co., Ltd.; tetrakis(2,4-di-t-butylphenyl)-4,4'-diphenylene- Di-phosphite]

(C) organopolyoxyalkylene compounds

‧Organic Oxane-1:KR-511 [trade name; manufactured by Nissho Shin-Etsu Chemical Co., Ltd.; organic polyoxyalkylene compound with phenyl, methoxy and vinyl groups]

‧Organic alkane-2: SH556 [trade name; Dongleidao Kangning Silicone Co., Ltd.; polymethylphenyl fluorene (branched)]

The results of the examples are shown in Table 1, and the results of the comparative examples are shown in Table 2.

As is clear from Table 1, any of the molded articles formed by the polycarbonate resin composition of the present invention can give good results.

On the other hand, the following items can be known from Table 2 showing the comparative example.

‧Comparative Example 1 in which no organic alkane was added, as compared with Example 1, it was found that the YI and the light transmittance were the same, but the generation of silver streaks which were defective in appearance could not be suppressed, and the mold was There are also many attachments.

‧ Comparative Example 2 in which the amount of the antioxidant added exceeds the upper limit of the present invention by 0.15 parts by mass, as compared with Example 4, it is understood that since the antioxidant is too much, the mold holder cannot be suppressed.

‧ When Comparative Example 3 using a polycarbonate having a low molecular weight and an organic oxetane-2 was used, it was found that the YI at the time of retention for 20 minutes was deteriorated as compared with Example 3. Further, it is understood that when the types of siloxanes are different, there is a large amount of silver streaks or molds which are poor in appearance.

‧ From Comparative Example 4 using organic oxetane-2, it was found that, in comparison with Example 3, YI was particularly deteriorated at 5 minutes and 20 minutes. Moreover, it can be seen that there are many silver streaks which are poor in appearance, and there are many molds attached.

‧ From Comparative Example 6 using Antioxidant-3, it was found that, in comparison with Example 3, YI was particularly deteriorated when it was retained for 20 minutes. Further, it can be seen that there are many silver streaks or molds which are poor in appearance.

‧ From Comparative Example 7 using the antioxidant-4, as compared with Example 3, it was found that YI was particularly deteriorated when it was retained for 20 minutes. Moreover, it can be seen that the mold is attached to a large amount.

‧Comparative Example 7 using a low molecular weight PC-5 and using antioxidant-1 and organodecane-1, compared with Examples 3 and 8, it can be seen that the generation of silver streaks is due to the high molecular weight component. Less, and the attachment of the mold occurs.

As described above, the polycarbonate, the phosphite represented by the formula (I) and/or (II), and the organopolydecane compound having a phenyl group, a methoxy group and a vinyl group are each blended in a predetermined amount. The polycarbonate resin composition constituting a remarkable double effect can be obtained.

Industrial use

The polycarbonate resin composition of the present invention is a polycarbonate resin composition which can reduce the occurrence of yellowing or crazing and the adhesion of a mold during molding under high temperature conditions, and has excellent release property and can be used as an electric appliance. Use of thin molded articles, light guide plates, films and sheets for electronic components, optical components, construction components, OA equipment, electrical and electronic equipment, and information communication equipment.

Claims (5)

A light guide plate which is formed by molding a polycarbonate resin composition which does not contain a light diffusing agent and which contains: the following general formula (I) and/or with respect to 100 parts by mass of polycarbonate Or (II) phosphite 0.01 to 0.15 parts by mass; and phenyl, methoxy and vinyl organic polyoxane compounds 0.01 to 0.15 parts by mass; In the formula (I), R ¹ represents an aryl group or an alkyl group, and may be the same or different; In the formula (II), R ⁹ is an alkyl group having 1 to 20 carbon atoms, and R ¹⁰ to R ¹⁴ are a hydrogen atom, an aryl group or an alkyl group having 1 to 20 carbon atoms, and each group may be the same or different. The light guide plate of claim 1, wherein the content of the phosphite and the organopolysiloxane compound is 0.03 to 0.1 parts by mass. The light guide plate of claim 1, wherein the acetone-soluble portion of the polycarbonate is 9% by mass or less. For example, the light guide plate of claim 1 is used for reflection on the back side. The white paint is formed into a dot-like or slit-like dense pattern by a printing process or a prismatic transfer. The light guide plate of the first aspect of the patent application is formed by prismatic transfer, which simultaneously forms a prismatic cut at the time of injection molding.