JP6397645B2 - Polycarbonate resin composition and molded body - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded body. More specifically, the polycarbonate resin composition has improved fluidity and color tone and excellent high-temperature molding stability, and is an optical molded product, particularly as a light guide plate. Useful polycarbonate resin composition and molded article using the same

  Aromatic polycarbonate resins are excellent in transparency, mechanical properties, thermal properties, electrical properties, weather resistance, and the like, and are used in optical molded products such as light guide plates, lenses, and optical fibers by taking advantage of the properties. Since materials for optical molded products are required to have high light guiding performance, development of copolymer polycarbonate resins and performance improvement by various additives have been performed. In recent years, display products with a larger screen and thinner thickness than conventional products such as smartphones and tablet PCs have become widespread, and further improvement in fluidity is required for the materials.

In order to increase the fluidity of the aromatic polycarbonate resin, for example, a method of lowering the molecular weight of the aromatic polycarbonate resin, or as disclosed in Patent Documents 1 and 2, a polyether diol such as polytetramethylene glycol is copolymerized A method for producing a polycarbonate resin composition by combining with the high-flow copolymerized polycarbonate resin has been proposed. However, when the fluidity is increased by such a method, there is a problem that the moisture resistance performance of the molded body is lowered. Furthermore, when a phosphite (phosphite) antioxidant is added to the aromatic polycarbonate resin to support high temperature molding, the phosphite antioxidant is easily hydrolyzed and processed into a light guide plate. Later, there was a problem that the light guide performance of the light guide plate deteriorated due to hydrolysis by a heat and humidity resistance test performed at a certain temperature and humidity conditions. In addition, the light guide plate using the low molecular weight polycarbonate resin having improved fluidity has a problem that after the moisture and heat resistance test, cracks are easily generated inside the light guide plate, and internal defects are easily generated.
Further, Patent Document 3 describes an optical recording medium using a polycarbonate having m-pentadecylphenoxy end groups, but the color tone is not sufficiently satisfactory.

JP 2009-298994 A JP 2009-40843 A JP 2003-41011 A

  An object of the present invention is to provide a polycarbonate resin composition having improved fluidity and color tone and excellent molding stability at high temperatures, and a molded product thereof.

The present invention relates to the following 1 to 15.
1. 1% by mass or less of the resorcinol derivative represented by the following general formula (I) and / or 2.5% by mass or less of the phenol derivative represented by the following general formula (II), the total content of the resorcinol derivative and the phenol derivative 380 nm light transmission in a 3 mm-thick molded product molded at 350 ° C. using a terminal stopper containing 3-pentadecylphenol having an amount of 2.5% by mass or less and a purity of 97.5% by mass or more as a raw material Polycarbonate resin (A) comprising 10-100% by mass of polycarbonate resin (A-1) having a rate of 85.0% or more, and 90-0% by mass of polycarbonate resin (A-2) other than (A-1). A polycarbonate resin composition containing 0.005 to 0.5 parts by mass of a phosphorus-based antioxidant (B) with respect to 100 parts by mass.

[In formula, R < ¹ >, R < ² > is a hydrogen atom or a C1-C20 aliphatic hydrocarbon group. R ³ is a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms. R ¹ , R ² and R ³ may be the same or different. However, in the above general formula (II), 3-pentadecylphenol represented by R ¹ = H and R ³ = C ₁₅ H ₃₁ is excluded. ]
2. 2. The polycarbonate resin composition according to 1 above, further containing (C) 0.001 to 0.5 parts by mass of an aliphatic cyclic epoxy compound with respect to 100 parts by mass of the component (A).
3. 3. The polycarbonate resin composition according to 1 or 2 above, wherein the purity of the 3-pentadecylphenol is 99.0% by mass or more.
4). 4. The polycarbonate resin composition according to any one of 1 to 3, obtained by crystallization after the 3-pentadecylphenol is distilled.
5. The polycarbonate resin composition according to any one of 1 to 4, wherein the content of 3-pentadecylphenoxy group in the component (A) is 0.1 to 10% by mass.
6). The polycarbonate resin composition according to any one of 1 to 5, wherein the component (B) has a pentaerythritol structure.
7). The polycarbonate resin composition according to any one of 1 to 6, wherein the component (B) is bis (2,4-dicumylphenyl) pentaerythritol diphosphite represented by the following general formula.

8). The component (C), 3,4-epoxy-cyclohexylene Rumechiru -3 ', 4'-epoxy cyclohexanol down carboxylate, 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy -4 The polycarbonate resin composition according to any one of 1 to 7, which is a-(2-oxiranyl) cyclohexane adduct and a mixture thereof.
9. The polycarbonate resin composition according to any one of 1 to 8, further comprising 0.02 to 0.15 parts by mass of a polyorganosiloxane (D) having a functional group with respect to 100 parts by mass of the component (A). .
10. 10. The function according to 9, wherein the functional group is at least one selected from the group consisting of an alkoxy group, an aryloxy group, a polyoxyalkylene group, a carboxyl group, a silanol group, an amino group, a mercapto group, an epoxy group, and a vinyl group. Polycarbonate resin composition.
11. The polycarbonate resin composition according to 9 or 10, wherein a difference between a refractive index of the polyorganosiloxane (D) having the functional group and a refractive index of the polycarbonate resin (A) is 0.13 or less.
12 The polycarbonate resin composition according to any one of 1 to 11, wherein the polycarbonate resin (A) has a viscosity average molecular weight of 8,000 to 19,000.
13. A molded body formed by molding the polycarbonate resin composition according to any one of 1 to 12 above.
14 14. The molded product according to 13, wherein the molded product is a light guide member.
15. 15. The molded product according to 14, wherein the light guide member is a light guide plate.

  ADVANTAGE OF THE INVENTION According to this invention, a fluidity | liquidity and a color tone are improved and the polycarbonate resin composition excellent in the molding stability at high temperature and a molded object can be provided.

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention comprises a polycarbonate resin (A) comprising 10 to 100% by mass of a polycarbonate resin (A-1) and 90 to 0% by mass of a polycarbonate resin (A-2) other than the above (A-1). It contains 0.005 to 0.5 parts by mass of the phosphorus-based antioxidant (B) with respect to 100 parts by mass. Hereinafter, the polycarbonate resin composition of the present invention will be described.

[Polycarbonate resin (A-1)]
The polycarbonate resin (A-1) contains 1% by mass or less of a resorcinol derivative represented by the following general formula (I) and / or 2.5% by mass or less of a phenol derivative represented by the following general formula (II). The total content of the derivative and the phenol derivative is 2.5% by mass or less and the purity is 97.5% by mass or more. .
It is preferable that 3-pentadecylphenol having a purity of 97.5% by mass or more used as a terminal stopper of the polycarbonate resin (A-1) is obtained from a natural product.
In the present specification, 3-pentadecylphenol having a purity of 97.5% by mass or more may be referred to as “high purity 3-pentadecylphenol”.

<High purity 3-pentadecylphenol>
The high purity 3-pentadecylphenol used in the present invention is required to have a purity of 97.5% by mass or more. When the purity is less than 97.5% by mass, the yellowness is high when used as a raw material for a polymer material such as a polycarbonate resin, and the transparency and appearance may be deteriorated. From the above viewpoint, the purity of the high purity 3-pentadecylphenol is preferably 99.0% by mass or more.
In order to obtain such high-purity 3-pentadecylphenol, an extract derived from a natural product of cashew nut shell liquid is used. In particular, it is efficient to use cardanol contained in a cashew nut shell liquid in an amount of about 10% by mass as a production raw material. Cardanol contained in cashew nut shell liquid is mainly 3-pentadecylphenol, 3-pentadecylphenol monoene, 3-pentadecylphenoldiene, and 3-pentadecylphenoltriene represented by the following general formula (III): It is a mixture of

In the above formula (III), when R ⁴ is — (CH ₂ ) ₁₄ CH ₃ , it is 3-pentadecylphenol, and R ⁴ is — (CH ₂ ) ₇ CH═CH (CH ₂ ) ₅ CH _3. Is 3-pentadecylphenol monoene, and when R ⁴ is — (CH ₂ ) ₇ CH═CHCH ₂ CH═CH (CH ₂ ) CH ₃ , it is 3-pentadecylphenol diene, When R ⁴ is — (CH ₂ ) ₇ CH═CHCH ₂ CH═CHCH ₂ CH═CH ₂ , it is 3-pentadecylphenoltriene.

As described above, the main component of cardanol contained in the cashew nut shell liquid is a phenol having a saturated bond and 1 to 3 unsaturated double bonds and having a hydrocarbon group having 15 carbon atoms in the 3-position (meta-position). It consists of a derivative.
In order to efficiently obtain high-purity 3-pentadecylphenol having a purity of 97.5% by mass or more used in the present invention, it is preferable to use cardanol contained in cashew nut shell liquid, and this cardanol is subjected to a hydrogenation reaction treatment. A method of increasing the purity by using crude pentadecylphenol (low purity pentadecylphenol) obtained by this is desirable. Alternatively, a method of directly purifying cashew nut shell liquid and using a crude pentadecylphenol obtained by distilling the obtained hydrogenation treatment liquid may be used. In addition, although commercially available pentadecylphenol is obtained by hydrogenating cardanol contained in cashew nut shell liquid, its purity is usually less than 97.5% by mass, so when using commercially available pentadecylphenol. It is necessary to increase the purity.

<Hydrogenation method>
In order to obtain 3-pentadecylphenol, it is desirable that the unsaturated bond (double bond) of the linear hydrocarbon portion of cardanol is hydrogenated and converted into a saturated bond as described above. In order to increase the purity of 3-pentadecylphenol in a state where a lot of unsaturated bonds are contained in the linear hydrocarbon portion, distillation or crystallization may have to be repeated, resulting in reduced productivity. Therefore, the conversion rate (hydrogenation rate) of unsaturated bonds by hydrogenation is preferably 90 mol% or more, and more preferably 95 mol% or more. The residual ratio of unsaturated bonds in cardanol after hydrogenation (number of unsaturated bonds per molecule of cardanol) is preferably 0.2 or less, more preferably 0.1 or less.
The method for hydrogenation is not particularly limited, and a normal method can be used. Examples of the catalyst include noble metals such as palladium, ruthenium, rhodium and platinum, or nickel or a metal selected from these metals supported on a support such as activated carbon, activated alumina or diatomaceous earth. As a reaction system, a batch system in which a reaction is performed while suspending and stirring a powdered catalyst, or a continuous system using a reaction tower filled with a molded catalyst can be employed. The solvent for hydrogenation may not be used depending on the method of hydrogenation. However, when a solvent is used, alcohols, ethers, esters, and saturated hydrocarbons are usually used. Although the reaction temperature in the case of hydrogenation is not specifically limited, Usually, 20-250 degreeC, Preferably it can set to 50-200 degreeC. If the reaction temperature is too low, the hydrogenation rate will be slow, whereas if it is too high, the decomposition products will tend to increase. The hydrogen pressure at the time of hydrogenation is usually normal pressure to 80 kgf / cm ² (normal pressure to 78.4 × 10 ⁵ Pa), preferably 3 to 50 kgf / cm ² (2.9 × 10 ^{5 to} 49.0). × 10 ⁵ Pa).

<Purification method>
The purity of the crude pentadecylphenol (low purity pentadecylphenol) obtained by the above hydrogenation treatment method is usually 90 to 93% by mass, and various resorcinol derivatives and phenol derivatives other than 3-pentadecylphenol as impurities. Contains.
In this specification, the resorcinol derivative is a compound having a structure having two OR groups (R = a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms) at the meta position of the benzene ring. And a phenol derivative is a compound having a structure having one OR group in the benzene ring.

As a method for obtaining high-purity 3-pentadecylphenol having a purity of 97.5% by mass or more used in the present invention, a method for purifying crude pentadecylphenol obtained by the hydrogenation treatment method described above by distillation. Examples thereof include a method for purification by crystallization, a method for purification by crystallization after distillation, and the like. In these, the method of crystallizing, after distilling crude pentadecyl phenol is preferable. Further, by using 3-pentadecylphenol having a purity of 97.5% by mass or more and further repeating distillation and crystallization, higher-purity 3-pentadecylphenol can be obtained.
As a method of purifying by distillation, for example, it can be purified by atmospheric distillation or vacuum distillation, and it is particularly preferable to purify by vacuum distillation. When purifying by vacuum distillation, the main fraction is preferably treated at a temperature of 200 to 260 ° C. and a pressure of 1 to 10 mmHg and treated with a filler in the vacuum distillation column. The flow rate / distillation amount) is preferably 0.5 to 10. As a filler used in the vacuum distillation column, a filler such as McMahon packing, Dixon packing, Raschig ring, ball ring, coil pack, helipak or the like can be used, but it is preferable to use McMahon packing.

As a method of purifying 3-pentadecylphenol by crystallization, the temperature of a solution in which crude pentadecylphenol is dissolved in a crystallization solvent is lowered in a crystallization tank to increase the purity of 3-pentadecylphenol. By utilizing the difference between the supersaturated state of the decylphenol solution and the saturated concentration of the compound, 3-pentadecylphenol is precipitated to form crystals of 3-pentadecylphenol, and then 3-pentadecylphenol in the crystalline state Is separated from the solution by solid-liquid separation, whereby high-purity 3-pentadecylphenol can be obtained. The crystallization operation can be performed in a wide temperature range from the boiling point to the melting point of the crystallization solvent used. The crystallization solvent is not particularly limited as long as it can dissolve 3-pentadecylphenol, and acetone, ethyl acetate, hydrocarbon solvents, acetonitrile, methanol, ethanol, and the like can be used. Among these, hydrocarbon solvents are preferable, and hexane and heptane are more preferable. The amount of the crystallization solvent can be appropriately set, but preferably 2 to 20 parts by mass, more preferably 4 to 10 parts by mass of the crystallization solvent is used with respect to 1 part by mass of 3-pentadecylphenol. It is possible to produce efficiently while ensuring the purity. Further, although crystallization is possible without adding seed crystals, crystallization can be efficiently performed by introducing seed crystals.
In addition, a controlled cooling method, a linear cooling method, a natural cooling method, and the like are known for reducing the temperature of a solution obtained by dissolving crude pentadecylphenol in a crystallization solvent in a crystallization tank, but the cooling method is particularly limited. In addition, the cooling rate can be appropriately set. Among them, the controlled cooling method reduces the temperature change at the initial stage when the amount of crystals is small (slow cooling rate), and increases the temperature change at the end of the period when the amount of crystals increases (faster the cooling rate). Since the supersaturation degree is kept low and constant throughout, secondary nucleation is suppressed and only monodisperse particles are obtained, which is preferable. The cooling rate is preferably set to 0 ° C. (constant temperature) to −10 ° C./h, more preferably 0 ° C. (constant temperature) to −5 ° C./h in the initial stage. The temperature is preferably lowered at −5 ° C./h to −30 ° C./h, more preferably −10 ° C. to −20 ° C./h.

By the purification method described above, 3-pentadecylphenol having a purity of 97.5% by mass or more can be obtained from crude pentadecylphenol.
In the high-purity 3-pentadecylphenol used in the present invention, a resorcinol derivative represented by the following general formula (I) is 1% by mass or less and / or a phenol derivative represented by the following general formula (II): It is necessary to contain 5% by mass or less and the total amount of the resorcinol derivative and the phenol derivative is 2.5% by mass or less. When the content of the resorcinol derivative and the phenol derivative is within the above range, the transparency and appearance of the polycarbonate resin (A-1) can be improved. In addition, when the purity of high-purity 3-pentadecylphenol is 99.0% by mass or more, the content of the resorcinol derivative is 0.8% by mass or less and / or the content of the phenol derivative is 0.8% by mass or less. And the total amount of the resorcinol derivative and the phenol derivative is desirably 0.8% by mass or less.

[In General Formula (I) and General Formula (II), R ¹ and R ² are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. R ³ is a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms. R ¹ , R ² and R ³ may be the same or different. However, in the above general formula (II), 3-pentadecylphenol represented by R ¹ = H and R ³ = C ₁₅ H ₃₁ is excluded. ]

R ¹ and R ² are aliphatic hydrocarbon groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. And alkyl groups such as dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. R ³ is a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, in addition to the alkyl groups exemplified for the above R ¹ and R ² , in addition to the carbon-carbon unsaturated divalent group. Examples thereof include an unsaturated aliphatic hydrocarbon group which is a monoene, diene or triene having one or more heavy bonds.
Examples of the compound contained in the general formula (I) include those in which R ¹ and R ² are hydrogen atoms, such as 5-pentadecylresorcinol, 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5 - butyl resorcinol, 5-hexylresorcinol, 5-octyl resorcinol, 5-decyl resorcinol, 5-dodecyl resorcinol, 5-tetradecyl resorcinol, 5-octadecyl resorcinol, 5-nonyl-decyl-resolution R ³ is from 1 to 20 carbon atoms, such as resorcinol And an unsaturated aliphatic hydrocarbon such as monoene, diene, and triene having one or more carbon-carbon unsaturated double bonds in the alkyl group. It may be a group.

In the general formula (I), R ¹ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom, and R ³ is a saturated or unsaturated fat having 1 to 20 carbon atoms. Examples of the compound which is an aromatic hydrocarbon group include 3-methoxy-5-pentadecylphenol, 3-ethoxy-5-pentadecylphenol, 3-propoxy-5-pentadecylphenol, 3-butoxy-5-pentadecylphenol 3-methoxy-5-hexylphenol, 3-methoxy-5-octylphenol, 3-methoxy-5-decylphenol, 3-methoxy-5-dodecylphenol, 3-methoxy-5-tetradecylphenol, 3-methoxy- 5-heptadecylphenol, 3-methoxy-5-octadecylphenol, 3-methoxy-5-nonyldecylpheno , 3-ethoxy-5-hexylphenol, 3-ethoxy-5-octylphenol, 3-ethoxy-5-decylphenol, 3-ethoxy-5-dodecylphenol, 3-ethoxy-5-tetradecylphenol, 3-ethoxy Examples thereof include compounds such as -5-heptadecylphenol, 3-ethoxy-5-octadecylphenol, and 3-ethoxy-5-nonyldecylphenol. It may be an unsaturated aliphatic hydrocarbon group such as monoene, diene or triene having one or more saturated double bonds.

The compound contained in the general formula (II) is a compound in which R ¹ is a hydrogen atom and R ³ is a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, such as 3-hexylphenol. Alkyl groups such as 3-octylphenol, 3-decylphenol, 3-dodecylphenol, 3-tridecylphenol, 3-tetradecylphenol, 3-hexadecylphenol, 3-octadecylphenol, 3-nonyldecylphenol, etc. Or an unsaturated aliphatic hydrocarbon group such as monoene, diene, or triene having one or more carbon-carbon unsaturated double bonds in the alkyl group or the alkyl group.
Examples of the compound in which R ¹ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms include 1-methoxy-3-hexylbenzene and 1-ethoxy-3-hexylbenzene when the 3-position is a hexyl group. 1-propoxy-3-hexylbenzene, 1-butoxy-3-hexylbenzene, 1-pentoxy-3-hexylbenzene, 1-hexoxy-3-hexylbenzene, 1-octoxy-3-hexylbenzene, 1-deoxy- Examples thereof include compounds such as 3-hexylbenzene, 1-dodeoxy-3-hexylbenzene, and 1-butyrodeoxy-3-hexylbenzene. When the 3-position is a pentadecyl group, 1-methoxy-3-pentadecylbenzene, 1-ethoxy-3-pentadecylbenzene, 1-propoxy-3-pentadecylbenzene, 1-butoxy-3-pentadecylbenzene, 1 -Pentoxy-3-pentadecylbenzene, 1-hexoxy-3-pentadecylbenzene, 1-octoxy-3-pentadecylbenzene, 1-decoxy-3-pentadecylbenzene, 1-dodecoxy-3-pentadecylbenzene, 1 Examples thereof include compounds such as -butyrodeoxy-3-pentadecylbenzene.

  In the general formulas (I) and (II), the exemplified alkyl group may be a linear alkyl group or a branched alkyl group.

<Polycarbonate resin (A-1)>
The polycarbonate resin (A-1) is preferably an aromatic polycarbonate resin, and the main chain includes a repeating unit represented by the following general formula (IV).
Polycarbonate resin (A-1) may be used individually by 1 type, and may use 2 or more types together.

Wherein, R ⁵ and R ⁶ are each independently a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, a carbon An arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O— or —CO—; a and b each independently represent an integer of 0 to 4. ]

Examples of the halogen atom independently represented by R ⁵ and R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group independently represented by R ⁵ and R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups (“various” means linear and all branched ones) And the same applies hereinafter), various pentyl groups, and various hexyl groups. Examples of the alkoxy group independently represented by R ⁵ and R ⁶ include a case where the alkyl group moiety is the alkyl group.
R ⁵ and R ⁶ are preferably both an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, and an alkylene group having 1 to 5 carbon atoms is preferable. Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group, and a cycloalkylene group having 5 to 10 carbon atoms is preferable. Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, 3,5,5-trimethylcyclohexylidene group, 2-adamantylidene group and the like, and a cycloalkylidene group having 5 to 10 carbon atoms is preferable. A cycloalkylidene group having 5 to 8 carbon atoms is more preferable.
Examples of the aryl moiety of the arylalkylene group represented by X and the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.
a and b each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1.

<Method for producing polycarbonate resin (A-1)>
Next, the manufacturing method of polycarbonate resin (A-1) is demonstrated. In order to produce the polycarbonate resin (A-1), it is necessary to use the high-purity 3-pentadecylphenol as a terminal group as a terminal stopper.
As the terminal stopper, a terminal stopper (other terminal stopper) other than high-purity 3-pentadecylphenol may be used in combination with high-purity 3-pentadecylphenol. As the other end terminator, a conventionally used end terminator for producing a polycarbonate resin can be used. For example, phenol, p-cresol, pt-butylphenol, p-cumylphenol, Examples include tribromophenol, nonylphenol, pt-octylphenol, and the like. Among these, pt-butylphenol and p-cumylphenol are preferable. When high purity 3-pentadecylphenol and other end terminator are used in combination, the use ratio thereof is preferably a molar ratio of (3-pentadecylphenol) :( other end terminator) is preferably 99: 1-20: 80, more preferably 90: 10-30: 70.

  In order to produce the polycarbonate resin (A-1), it is necessary to use a dihydric phenol for constituting the main chain. Various known dihydric phenols can be used as the dihydric phenol, but it is preferable to use a dihydric phenol represented by the following general formula (1).

Here, in said general formula (1), R < ⁵ >, R < ⁶ >, X, a, and b are the same as the above.
The dihydric phenol represented by the general formula (1) is not particularly limited, but 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is preferable.
Examples of dihydric phenols 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) naphthylmethane, 1,1-bis (4-hydroxy-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) Bis (hydroxyaryl) alkanes such as propane, 2,2-bis (4-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-trimethylcyclohexane, 2,2- Bis (hydroxyaryl) cycloalkanes such as bis (4-hydroxyphenyl) norbornane and 1,1-bis (4-hydroxyphenyl) cyclododecane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3, Dihydroxy aryl ethers such as 3′-dimethylphenyl ether, 4,4′-dihy Roxydiphenyl sulfide, dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide Dihydroxydiaryl sulfoxides such as 4,4′-dihydroxydiphenylsulfone, dihydroxydiarylsulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, and dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl Dihydroxydiarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis (4-hydroxyphenyl) ada Dihydroxydiaryladamantanes such as lanthanum, 2,2-bis (4-hydroxyphenyl) adamantane, 1,3-bis (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-dioxapentane, and the like. It is done.
These dihydric phenols may be used alone or in admixture of two or more.

  Further, as a dihydric phenol not contained in the dihydric phenol represented by the general formula (1), a dihydric phenol containing a structural unit represented by the following general formula (2) is represented by the above general formula (1). Can be used in combination with the dihydric phenol. By setting it as the copolymer which has such a structural unit, the flame retardance and impact resistance of the polycarbonate resin (A-1) obtained can be improved. The dihydric phenol containing the structural unit represented by the following general formula (2) is represented by a polyorganosiloxane represented by the following general formula (2-1).

In the general formula (2) or the general formula (2-1), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. -6 alkoxy group or a C6-C12 aryl group is shown. Z represents a phenol residue having a trimethylene group, which is derived from a phenol compound having an allyl group. n shows 70-1000.
The polyorganosiloxane represented by the general formula (2-1) is obtained by modifying the terminal of a polyorganosiloxane having a terminal hydrogen with a phenol compound having an allyl group at the terminal, such as 2-allylphenol and eugenol. It is. A polyorganosiloxane modified with a phenol compound having an allyl group at the terminal can be synthesized by the method described in Japanese Patent No. 2662310.
As the polyorganosiloxane, polydimethylsiloxane is preferred.

Furthermore, a branching agent may be used in the main chain of the polycarbonate resin by using a branching agent for the dihydric phenol. The addition amount of the branching agent is preferably 0.01 to 3 mol%, more preferably 0.1 to 1.0 mol%, based on the dihydric phenol.
Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane and 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]- Examples include compounds having three or more functional groups such as 4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, phloroglucin, trimellitic acid, and isatin bis (o-cresol).

The polycarbonate resin (A-1) is produced by reacting a carbonate raw material with a dihydric phenol. A carbonate raw material is a compound which can produce | generate a carbonate bond in a polycarbonate principal chain by polymer production | generation reactions, such as a condensation reaction and an exchange reaction. Such compounds include phosgene, triphosgene, bromophosgene, bis (2,4,6-trichlorophenyl) carbonate, bis (2,4-dichlorophenyl) when polycarbonate is produced by the interfacial polycondensation method. Examples thereof include phosgene derivatives such as carbonate, bis (2-cyanophenyl) carbonate, and trichloromethyl chloroformate.
Further, in the production of polycarbonate by a transesterification method (melting method), a carbonate diester is used as the carbonate raw material, and examples of the carbonate diester include a diaryl carbonate compound, a carbon dialkyl compound, and an alkylaryl carbonate compound.
Here, specific examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, bisphenol A bisphenyl carbonate, and the like. . Specific examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate, and the like. Specific examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A methyl phenyl carbonate, and the like.

The polycarbonate resin (A-1) is produced by a method commonly used in the production of a normal polycarbonate resin, for example, an interfacial polycondensation method using phosgene or a phosgene derivative, and a transesterification method (melting method). Of these, interfacial polycondensation is preferred.
As an interfacial polycondensation method using phosgene or a phosgene derivative, for example, a polycarbonate oligomer of the dihydric phenol is synthesized in advance from the dihydric phenol and phosgene or a phosgene derivative, and an inert organic solvent solution of the oligomer is used. A method of reacting by adding an aqueous alkali solution containing the dihydric phenol and a terminal stopper containing the high-purity 3-pentadecylphenol, or an aqueous alkali solution of the dihydric phenol and the high-purity 3-pentadecylphenol Examples thereof include a method in which phosgene or a phosgene derivative is added to a mixed liquid of a terminal terminator and an inert organic solvent and reacted, and among these, the former oligomer method is preferable.

  Next, a method for producing the polycarbonate resin (A-1) by the oligomer method will be described. First, the dihydric phenol is dissolved in an aqueous solution of an alkali metal hydroxide, and an alkaline aqueous solution of dihydric phenol (such as sodium hydroxide). The aqueous solution). Subsequently, phosgene or a phosgene derivative is introduced into a mixed solution of the alkaline aqueous solution and an inert organic solvent (an organic solvent such as methylene chloride) to synthesize the polycarbonate oligomer of the dihydric phenol. At this time, the alkali concentration of the aqueous alkali solution is preferably in the range of 1 to 15% by mass, and the volume ratio of the organic phase to the aqueous phase is usually 5: 1 to 1: 7, preferably 2: 1 to 1: 4. It is desirable to be in range. The reaction temperature is cooled in a water bath and is usually selected in the range of 0 to 50 ° C., preferably 5 to 40 ° C., and the reaction time is usually about 15 minutes to 4 hours, preferably about 30 minutes to 2 hours. The degree of polymerization of the polycarbonate oligomer thus obtained is usually 20 or less, preferably about 2 to 10.

Next, the organic phase containing the polycarbonate oligomer thus obtained is added with an alkali aqueous solution of the dihydric phenol, a terminal terminator containing the high-purity 3-pentadecylphenol, and an inert organic solvent as required, followed by stirring. The contact polycondensation is usually carried out at a temperature in the range of 0 to 50 ° C., preferably 5 to 40 ° C., usually for about 10 minutes to 6 hours. At this time, the alkali concentration of the aqueous alkali solution is preferably 1 to 15% by mass, and the volume ratio of the organic phase to the aqueous phase is usually 7: 1 to 1: 2, preferably 4: 1 to 1: 1. It is desirable. The ratio of the dihydric phenol to the polycarbonate oligomer is such that the molar ratio of (dihydric phenol) / (chloroformate group of the polycarbonate oligomer) is usually 0.4 to 0.55, preferably 0.45 to 0. .5 is chosen. The ratio of alkali metal hydroxide to polycarbonate oligomer is such that the molar ratio of (alkali metal hydroxide) / (chloroformate group of polycarbonate oligomer) is usually 1.0 to 2.0, preferably 1. It is chosen to be 2 to 1.7. Further, the amount of the terminal stopper used is such that the molar ratio of (terminal stopper) / (chloroformate group of polycarbonate oligomer) is usually 0.02 to 0.20, preferably 0.04 to 0.17. So chosen. Furthermore, in this reaction, a catalyst can be used as desired. The molar ratio of (catalyst) / (polycarbonate oligomer chloroformate group) is usually 1.0 × 10 ^{−3 to} 10.0 × 10 ⁻³ , preferably 1.0 × 10 ^−3. It is selected to be ˜5.0 × 10 ⁻³ .

  Examples of the alkali metal hydroxide used in the production of the polycarbonate resin (A-1) include sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide. Of these, sodium hydroxide and potassium hydroxide are preferred. There are various kinds of inert organic solvents. For example, dichloromethane (methylene chloride); chloroform; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; 1,1,2-trichloroethane; 1,1,1,2-tetrachloroethane; 1,2,2,2-tetrachloroethane; chlorinated hydrocarbons such as pentachloroethane and chlorobenzene, and acetophenone. These organic solvents may be used alone or in combination of two or more. Among these, chloroform and methylene chloride are preferable, and methylene chloride is particularly preferable.

Various catalysts can be used as the catalyst. Specific examples include quaternary ammonium salts, quaternary phosphonium salts, and tertiary amines. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide and the like. Examples of the quaternary phosphonium salt include tetrabutylphosphonium chloride and tetrabutylphosphonium bromide. Examples of the tertiary amine include triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, and dimethylaniline. Etc.
Among the catalysts, tertiary amines are preferable, and triethylamine is particularly preferable. From the organic solvent solution containing the polycarbonate resin thus obtained, the polycarbonate resin (A-1) can be obtained by performing a recovery operation according to a usual method.

  In the production of a polycarbonate resin by a transesterification reaction method (melting method), a dihydric phenol, a carbonic acid diester, and a terminal terminator containing the high-purity 3-pentadecylphenol, and a branching agent, if necessary, are used. The polycarbonate resin (A-1) can be obtained by causing a transesterification reaction in a molten state and removing by-produced phenol out of the system under reduced pressure conditions or the like. In the transesterification reaction method, a transesterification catalyst may be used to accelerate the reaction. As the transesterification catalyst, salts such as sodium, calcium and cesium, ammonium salts, and phosphonium salts are preferable.

The polycarbonate resin (A-1) is obtained using high-purity 3-pentadecylphenol as a terminal terminator and has a terminal group derived from 3-pentadecylphenol.
The polycarbonate resin (A-1) has a 380 nm light transmittance of 85.0% or more in a 3 mm-thick molded body molded at 350 ° C. When the light transmittance of 380 nm is 85.0% or more, it can be suitably used for a light guide member for liquid crystal that requires transparency, and further for a light guide member for liquid crystal having a thin and large screen. From the above viewpoint, the 380 nm light transmittance is preferably 86% or more, and more preferably 87% or more.
The viscosity average molecular weight of the polycarbonate resin (A-1) is not particularly limited, but is preferably 8,000 to 19,000, from the viewpoint of maintaining fluidity and strength when molding a thin molded product. More preferably, it is 9,000 to 17,000, and further preferably 10,000 to 15,000.
The yellow index (YI) of the polycarbonate resin (A-1) is preferably 1.5 or less. When the YI of the polycarbonate resin (A-1) is 1.5 or less, it is excellent in color tone and can be suitably used for a liquid crystal member that requires transparency. From the above viewpoint, the YI of the polycarbonate resin (A-1) is more preferably 1.3 or less, and still more preferably 1.1 or less.

[Polycarbonate resin (A-2)]
The polycarbonate resin composition of the present invention may contain a polycarbonate resin (A-2) other than the polycarbonate resin (A-1).
There is no restriction | limiting in particular as said polycarbonate resin (A-2), Although various well-known polycarbonate resins can be used, Aromatic polycarbonate resin is preferable.
From the viewpoint of physical properties, the viscosity average molecular weight of the component (A-2) polycarbonate-based resin is preferably 10,000 to 40,000, more preferably 11,000 to 17,000.

  The aromatic polycarbonate resin preferably has a main chain composed of repeating units represented by the following general formula (V).

[In formula, R < ⁹ > and R < ¹⁰ > shows a halogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group each independently. X ′ is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO. -, - SO ₂ -, - indicating O- or -CO- a. d and e each independently represent an integer of 0 to 4. ]
Specific examples of R ⁹ and R ¹⁰ include the same as R ⁵ and R ⁶ . R ⁹ and R ¹⁰ are preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Specific examples of X ′ include the same as X described above, and preferable examples are also the same. d and e are each independently preferably 0 to 2, more preferably 0 or 1.

Specifically, the aromatic polycarbonate resin is prepared by reacting with an aromatic dihydric phenol compound and phosgene in the presence of an organic solvent inert to the reaction, an aqueous alkaline solution, and then a tertiary amine or quaternary ammonium. Conventional methods such as an interfacial polymerization method in which a polymerization catalyst such as a salt is added and polymerized, and a pyridine method in which an aromatic dihydric phenol compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is directly introduced, etc. Those obtained by the method for producing an aromatic polycarbonate can be used.
In the above reaction, a molecular weight regulator (terminal terminator), a branching agent and the like are used as necessary.
In addition, as said aromatic dihydric phenol type compound, what is represented by following General formula (3) is mentioned.

[Wherein, R ⁹ , R ¹⁰ , X ′, d and e are as defined above, and preferred ones are also the same. ]
Specific examples of the aromatic dihydric phenol compound include the same divalent phenol represented by the general formula (1), and preferred ones are also the same. Further, as the dihydric phenol not contained in the dihydric phenol represented by the general formula (3), the dihydric phenol containing the structural unit represented by the general formula (2) is used. The polyorganosiloxane represented by 1) can be used in combination with the dihydric phenol represented by the general formula (3).
The said bihydric phenol may be used individually by 1 type, and may use 2 or more types together.

Examples of the branching agent include those exemplified above.
As the terminal stopper, a conventionally used terminal stopper for producing a polycarbonate resin can be used, and examples thereof include phenol, p-cresol, pt-butylphenol, p-cumylphenol, and tribromo. Phenol, nonylphenol, pt-octylphenol and the like can be mentioned. Among these, pt-butylphenol and p-cumylphenol are preferable.

[Polycarbonate resin (A)]
The polycarbonate resin (A) is composed of 10 to 100% by mass of the polycarbonate resin (A-1) and 90 to 0% by mass of the polycarbonate resin (A-2).
Content of the said polycarbonate resin (A-1) is 10-100 mass% in (A) component, Preferably it is 30-100 mass%, More preferably, it is 50-100 mass%, More preferably, it is 70-100 mass%. It is.
When the polycarbonate resin (A-2) other than the component (A-1) is contained in the polycarbonate resin composition of the present invention, the content thereof is 90% by mass or less, preferably 70% by mass in the component (A). % Or less, More preferably, it is 50 mass% or less, More preferably, it is 30 mass% or less.
The content of 3-pentadecylphenoxy group in the component (A) is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and still more preferably 0.8 to 7% by mass. is there. If content of 3-pentadecylphenoxy in (A) component is the said range, while fluidity | liquidity will improve and color tone will improve, durability will improve.
The viscosity average molecular weight of the polycarbonate resin (A) is not particularly limited, but is preferably 8,000 to 19,000, more preferably from the viewpoint of maintaining fluidity and strength when molding a thin molded product. Is preferably in the range of 9,000 to 17,000, more preferably 10,000 to 15,000.

[Phosphorus antioxidant (B)]
The polycarbonate resin composition of the present invention contains a phosphorus-based antioxidant (B). By containing the phosphorus-based antioxidant (B), it is possible to suppress an increase in the YI value of the polycarbonate resin composition, and even if the resin composition stays at a high temperature during the molding process, a good color tone can be maintained. Excellent processing stability can be imparted to the polycarbonate resin composition.

  As the phosphorus-based antioxidant, phosphorous acid, phosphonous acid, phosphonic acid and esters thereof, tertiary phosphine, and the like can be used. Among them, those having a pentaerythritol structure are preferable, and phosphites having a pentaerythritol structure represented by the following general formula (4) are more preferable.

In the general formula (4), R ⁷ and R ⁸ each represent hydrogen, an alkyl group, a cycloalkyl group, or an aryl group. In addition, the cycloalkyl group and the aryl group may be substituted with an alkyl group.
When R ⁷ and R ⁸ are aryl groups, R ⁷ and R ⁸ are preferably aryl groups represented by the following general formula (a), (b) or (c).

[In formula (a), R ⁹ represents an alkyl group having 1 to 10 carbon atoms. ]

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

  Specific examples of the phosphite ester having a pentaerythritol structure represented by the general formula (4) include bis (2,6-di-tert-butyl-4-methylphenyl) represented by the following general formula (5). In addition to pentaerythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite of the following general formula (6), compounds of the following general formulas (7) to (10) can be exemplified. .

  Among these, as the phosphorus-based antioxidant (B), bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite of the general formula (5) [for example, ADK STAB PEP -36: manufactured by ADEKA Corporation], and bis (2,4-dicumylphenyl) pentaerythritol diphosphite of the general formula (6) [for example, Doverphos S-9228PC: manufactured by Dover Chemical Corporation] is preferable. The bis (2,4-dicumylphenyl) pentaerythritol diphosphite of the general formula (6) is more preferable.

  In the polycarbonate resin composition of the present invention, the content of the phosphorus-based antioxidant (B) is 0.005 to 0.5 parts by mass, preferably 0.01 with respect to 100 parts by mass of the component (A). It is -0.2 mass part, More preferably, it is 0.02-0.1 mass part. If the amount is less than 0.005 parts by mass, an increase in the YI value cannot be suppressed, and a good color tone cannot be maintained if the resin composition is retained at a high temperature during the molding process. On the other hand, when the amount exceeds 0.5 parts by mass, hydrolysis of the polycarbonate by the decomposition product is promoted, and desired performance cannot be expressed.

[Aliphatic cyclic epoxy compound (C)]
The polycarbonate resin composition of this invention can contain an aliphatic cyclic epoxy compound (C) as needed.
Examples of the aliphatic cyclic epoxy resin (C) include compounds in which a part of the structure is epoxidized. By including the aliphatic cyclic epoxy compound (C) in the polycarbonate resin composition of the present invention, the durability of the molded article can be improved.
Such alicyclic epoxy compound Among (C), 3,4-epoxy-cyclohexylene Rumechiru -3 ', 4'-epoxy cyclohexanol down carboxylate (Daicel Chemical Industries Co., Ltd. under the trade name "CELLOXIDE 2021P", etc.) 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (trade name “EHPE3150” manufactured by Daicel Chemical Industries, Ltd.), A mixture (trade name EHPE3150CE manufactured by Daicel Chemical Industries, Ltd.) is preferred.

  The content of the aliphatic cyclic epoxy compound (C) in the polycarbonate resin composition of the present invention is preferably 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the component (A). When the content is 0.001 part by mass or more, the durability is sufficiently improved, and when it is 0.5 part by mass or less, white turbidity is suppressed and the color tone is improved. From the above viewpoint, the content of the aliphatic cyclic epoxy compound (C) is more preferably 0.005 to 0.3 parts by mass, and still more preferably 0.01 to 0.1 parts by mass.

[Polyorganosiloxane having functional group (D)]
The polycarbonate resin composition of this invention can contain the polyorganosiloxane (D) which has a functional group as needed.
The polyorganosiloxane having the functional group is at least one functional group selected from the group consisting of alkoxy groups, aryloxy groups, polyoxyalkylene groups, carboxyl groups, silanol groups, amino groups, mercapto groups, epoxy groups, and vinyl groups. It preferably has a group.

The viscosity of the polyorganosiloxane (D) having the above functional group is preferably 10 mm ² / sec or more at 25 ° C. from the viewpoint of lubricity effect, and more from the viewpoint of dispersibility in the polycarbonate resin (A). Preferably, it is 200 mm ² / sec or less. In view of the above, the viscosity range of the polyorganosiloxane (D) having the functional group is more preferably 20 to 150 mm ² / s, particularly preferably 40~120mm ² / sec.

  In order that the refractive index of the polyorganosiloxane (D) having the functional group does not decrease the transparency of the polycarbonate resin composition of the present invention, the difference in refractive index from the polycarbonate resin (A) is preferably as small as possible. . From the above viewpoint, the difference between the refractive index of the polyorganosiloxane (D) having the functional group and the refractive index of the polycarbonate resin (A) is preferably 0.13 or less, more preferably 0.08 or less. More preferably, it is 0.05 or less. Further, since the refractive index of the polycarbonate resin is about 1.58, the refractive index of the polyorganosiloxane (D) having the functional group is preferably 1.45 or more, more preferably 1.50 or more, and still more preferably. Is 1.51 or more.

  The content of the polyorganosiloxane (D) having a functional group in the polycarbonate resin composition of the present invention is preferably 0.02 to 0.15 parts by mass, more preferably 100 parts by mass with respect to the polycarbonate resin (A). Is 0.03-0.12 parts by mass. If content of (D) component mix | blends in said range, a mold release property can be improved with another component. Furthermore, even under high-temperature molding conditions that greatly exceed 300 ° C., particularly continuous molding conditions, it is possible to significantly reduce the generation of silver and the deposits on the mold.

[Polycarbonate resin composition / molded body]
The polycarbonate resin composition of the present invention has the effects of the present invention in addition to the component (A) and the component (B) described above and the component (C) and the component (D) added as necessary. In the range which does not impair the above, conventionally known various additives which are conventionally added to the polycarbonate resin composition can be blended as required.
These additives include antioxidants other than phosphorus antioxidants, UV absorbers, flame retardants, mold release agents, inorganic fillers (glass fibers, talc, titanium oxide, mica, etc.), colorants, light diffusion Agents and the like.

The molded body made of the polycarbonate resin composition of the present invention can be obtained by molding and kneading the above-mentioned components.
The kneading method is not particularly limited, and examples thereof include a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a kneader, a multi screw extruder, and the like. . Moreover, the heating temperature at the time of kneading | mixing is 240-330 degreeC normally, Preferably it is selected in 250-320 degreeC.
As the molding method, conventionally known various molding methods can be used, 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. It is done.

In addition, the components other than the polycarbonate resin can be added in advance as a masterbatch by melt-kneading with the polycarbonate resin or other thermoplastic resin.
Further, it is preferably pelletized and injection molded, and special molding methods such as general injection molding method or injection compression molding method and gas assist molding method can be used, and various molded products can be produced. .
The molded body formed by molding the polycarbonate resin composition of the present invention can be suitably used as a resin for a light guide member or a light diffusion plate. As the light guide member, a light guide member for a liquid crystal device such as a light guide plate of a liquid crystal display device used in a mobile phone, a liquid crystal television, a personal computer, an electronic dictionary, an electronic book, a smartphone, a tablet PC, etc., a daytime attached to a headlamp The light guide member used for a running light, LED lighting, etc. is mentioned. Since the polycarbonate resin composition of the present invention is excellent in fluidity, it is desirable to form it by injection molding, particularly when producing a thin molded body, and a resin for a light guide plate or a light diffusion plate of a liquid crystal display device. Can be suitably used.

  The following examples further illustrate the present invention. Note that the present invention is not limited to these examples. In addition, the measurement evaluation in an Example and a comparative example was performed by the method shown below.

<Measurement method of purity and impurity amount of 3-pentadecylphenol>
3-Pentadecylphenol and resorcinol derivative were manufactured by Agilent Technologies; “AGILENT 1200”, “L-column ODS” (4.6 mm ID × 150 mm, particle size 3 μm) in column, acetonitrile / formic acid buffer in mobile phase = It measured using 95/5 (vol / vol).
The phenol derivative was measured by “JMS-Q1000GC” manufactured by JEOL Ltd. using a column “VF-1” having a length of 30 m, an inner diameter of 250 μm, and a film thickness of 0.25 μm.

<Measurement of viscosity number (VN)>
The viscosity number (VN) of the polycarbonate resin was measured according to ISO 1628-4 (1999).
<Measurement of viscosity average molecular weight (Mv)>
The viscosity average molecular weight (Mv) of the polycarbonate resin is obtained by measuring the viscosity of the methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, obtaining the intrinsic viscosity [η] from this, and calculating by the following formula. .
[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83

<Measurement of light transmittance>
To 100 parts by mass of the obtained polycarbonate resin, 500 mass ppm of ADK STAB PEP36 [manufactured by ADEKA Corporation, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite] was added, and 40 mmφ with vent Was melt-kneaded and extruded at a resin temperature of 280 ° C. and a screw rotation speed of 100 rpm using a single-screw extruder, and pellets were obtained. The measurement was performed with a U-4100 spectrophotometer manufactured by Hitachi High-Technologies Corporation. The acceptance criterion is that the transmittance at 380 nm is 85% or more.

<Measurement of end group composition amount>
JEOL Ltd .; ¹ J-NMR was measured using “JNM-LA500” to calculate the terminal group composition of the polycarbonate resin. Moreover, content (mass%) of 3-pentadecyl phenoxy group in polycarbonate resin was computed from the terminal group composition amount.

Preparation Example 1
McMahon Packing (Mc. MAHON Packing, standard size: 6 mm) is packed in a column with an inner diameter of 30 mm and a volume of 500 mL to form a rectification column, which is attached to a 2 L flask equipped with an internal temperature measuring device, and a reflux ratio ( A device for adjusting the reflux amount / distillation amount), a device for measuring the tower top temperature, and a depressurization degree adjusting device were attached. 100.96 g of 3-pentadecylphenol (manufactured by Tokyo Chemical Industry Co., Ltd., purity 92.10% by mass, resorcinol derivative: 2.15% by mass, phenol derivative 5.11% by mass) was supplied to the flask, and after nitrogen substitution, Heating decompression was started. The degree of pressure reduction was set to 2 mmHg, the reflux amount / distillation amount = 1, and the fraction having a tower top temperature of 205 to 210 ° C. was fractionated. At this time, the flask temperature was 230-245 degreeC. The amount collected was 825.71 g (82% by mass of the charge), and the purity of 3-pentadecylphenol was 93.61% by mass.
Next, the obtained crude 3-pentadecylphenol was melted in a 60 ° C. hot water bath and weighed 70 g in a standard bottle, and 420 g of n-hexane was added and dissolved. After leaving still at room temperature for 12 hours and filtering the depositing solid under reduced pressure, 48 g of corresponding 3-pentadecyl phenol was obtained by drying under reduced pressure at room temperature for 8 hours. The 3-pentadecylphenol content in the obtained 3-pentadecylphenol was 97.75% by mass. 70 g of 3-pentadecylphenol having a purity of 97.75% by mass was melted in a 60 ° C. hot water bath and weighed 70 g in a standard bottle, and then 420 g of n-hexane was added and dissolved. After leaving still at room temperature for 12 hours and filtering the depositing solid under reduced pressure, it dried under reduced pressure at room temperature for 8 hours, and 54 g of 3-pentadecyl phenol with a purity of 99.33 mass% was obtained. The content of resorcinol derivative in the obtained 3-pentadecylphenol was 0.23% by mass, and the phenol derivative was 0.02% by mass.

Production Example 1
[Production of polycarbonate resin (A-1)]
(1) Production of polycarbonate oligomer 0.2% by mass of sodium dithionite with respect to bisphenol A (BPA) to be dissolved later is added to a 5.6% by mass sodium hydroxide aqueous solution, and the BPA concentration is 13 BPA was dissolved so that it might become 5 mass%, and the sodium hydroxide aqueous solution of BPA was prepared. A sodium hydroxide aqueous solution of BPA was continuously passed through a tubular reactor having an inner diameter of 6 mm and a pipe length of 30 m at a flow rate of 40 L / hr and methylene chloride at a flow rate of 15 L / hr, and phosgene was continuously supplied at a flow rate of 4.0 kg / hr. Passed through. The tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C. or lower by passing cooling water through the jacket.
The reaction liquid sent out from the tubular reactor was continuously introduced into a 40-liter baffled tank reactor equipped with a receding blade, and further BPA sodium hydroxide aqueous solution was added at 2.8 L / hr, 25 mass% sodium hydroxide aqueous solution 0.07 L / hr, water 17 L / hr, 1 mass% triethylamine aqueous solution 0.64 L / hr, 20 mass% pt-butylphenol (PTBP) methylene chloride solution 149. The reaction was carried out at 29 to 32 ° C. at a flow rate of 2 kg / hr. The reaction liquid was continuously extracted from the tank reactor and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected. The polycarbonate oligomer solution thus obtained had an oligomer concentration of 321 g / L and a chloroformate group concentration of 0.75 mol / L.

(2) Production of polycarbonate resin The above-mentioned oligomer solution 19L and methylene chloride 11L were charged into a 50 L tank reactor equipped with baffle plates and paddle type stirring blades, and the purity obtained in Preparation Example 1 was 99.33% by mass. After dissolving 361 g of 3-pentadecylphenol (m-PDP) and 64 g of PTBP, 5.6 mL of triethylamine was added, and 1814 g of a 6.4% by mass aqueous sodium hydroxide solution was added thereto with stirring, and the reaction was performed for 10 minutes. It was. BPA aqueous solution of sodium hydroxide (701 g of NaOH and 2.9 g of sodium dithionite dissolved in 10.8 L of water in which 1462 g of BPA was dissolved) was added, and a polymerization reaction was carried out for 50 minutes.
For dilution, 4 L of methylene chloride was added and stirred for 10 minutes. Then, the organic phase was separated into an organic phase containing polycarbonate and an aqueous phase containing excess bisphenol A and NaOH, and the organic phase was isolated. The obtained methylene chloride solution of the polycarbonate resin was washed with 15 vol% 0.03 mol / L aqueous sodium hydroxide solution and 0.2 mol / L hydrochloric acid successively with respect to the solution, and then the electric conduction in the aqueous phase after washing. The washing was repeated with pure water until the degree became 0.5 mS / m or less. The methylene chloride solution of the polycarbonate resin obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 100 ° C. under reduced pressure to obtain a polycarbonate resin. The composition ratio of m-PDP determined by ¹ H-NMR was 4.07 mol%, and the composition ratio of PTBP was 4.24 mol%. The polycarbonate resin had a light transmittance of 87.95% at 380 nm.

Production Example 2
[Production of polycarbonate resin (A-1)]
A polycarbonate resin was obtained in the same manner as in Production Example 1 except that PTBP 64 g was not used in the production of (2) polycarbonate resin in Production Example 1. The composition ratio of m-PDP determined by ¹ H-NMR was 4.08 mol%, and the composition ratio of PTBP was 2.89 mol%. The polycarbonate resin had a light transmittance of 87.90% at 380 nm.

Production Example 3
[Production of polycarbonate resin (A-1)]
Production method 1 (2) In the production of polycarbonate resin, the same method as in Production example 1 except that the amount of m-PDP used was changed from 361 g to 72 g and the amount of PTBP used was changed from 64 g to 171 g. Thus, a polycarbonate resin was obtained. The composition ratio of m-PDP determined by ¹ H-NMR was 0.80 mol%, and the composition ratio of PTBP was 6.74 mol%. The polycarbonate resin had a 380 nm light transmittance of 86.92%.

Production Example 4
[Production of polycarbonate resin (A-1)]
In the production of (2) polycarbonate resin in Production Example 1, the same method as in Production Example 1 except that the amount of m-PDP used was changed from 361 g to 217 g and the amount of PTBP used was changed from 64 g to 100 g. Thus, a polycarbonate resin was obtained. The composition ratio of m-PDP determined by ¹ H-NMR was 2.41 mol%, and the composition ratio of PTBP was 5.14 mol%. The polycarbonate resin had a light transmittance of 380 nm of 87.60%.

Production Example 5
[Production of polycarbonate resin (A-1)]
A polycarbonate resin was obtained in the same manner as in Production Example 1 except that the amount of PTBP used was changed from 64 g to 29 g in the production of (2) polycarbonate resin in Production Example 1. The composition ratio of m-PDP determined by ¹ H-NMR was 4.06 mol%, and the composition ratio of PTBP was 3.27 mol%. The polycarbonate resin had a 380 nm light transmittance of 87.86%.

Examples 1-14, Comparative Examples 1-4
[Production of polycarbonate resin composition]
To 100 parts by mass of the polycarbonate resin (A) described in Table 1, 0.05 part by mass of the phosphorus-based antioxidant (B) described in Table 1 is blended, and the aliphatic cyclic epoxy compound (C ) And a polyorganosiloxane (D) having a functional group are blended in the proportions shown in Table 1, and melt-kneaded and extruded at a resin temperature of 280 ° C. and a screw rotation speed of 1000 ppm using a 40 mmφ single-screw extruder with a vent, and granulation As a result, pellets of the polycarbonate resin composition were obtained.
The molding material used and the performance evaluation method of the molded body are shown below. The results are shown in Table 1.

(A-1) Component “PDP1100-5” Polycarbonate resin obtained in Production Example 1 “PDP1300-5” Polycarbonate resin obtained in Production Example 2 “PDP1200-1” Polycarbonate resin obtained in Production Example 3 “PDP1200” -3 "polycarbonate resin obtained in Production Example 4" PDP1200-5 "Polycarbonate resin (A-2) component obtained in Production Example 5" Taflon FN1200 "(Idemitsu Kosan Co., Ltd., bisphenol A polycarbonate resin, viscosity Average molecular weight (Mv) = 11500)
“Taflon FN1500” (made by Idemitsu Kosan Co., Ltd., bisphenol A polycarbonate resin, viscosity average molecular weight (Mv) = 14500)
(B) Component “Adeka Stab PEP-36” (manufactured by ADEKA, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite)
“Doverphos S-9228PC” (manufactured by Dover Chemical, bis (2,4-dicumylphenyl) pentaerythritol diphosphite)
Component (C) "CELLOXIDE 2021P" (manufactured by Daicel Chemical Industries, Ltd., 3,4-epoxy-cyclohexylene Rumechiru -3 ', 4'-epoxy cyclohexanol down carboxylate)
(D) Component “KR511” (manufactured by Shin-Etsu Silicone Co., Ltd., organopolysiloxane having a methoxy group, a phenyl group and a vinyl group, refractive index = 1.518)

[Performance evaluation]
(1) MVR
The pellets obtained by the above method, Yasuda Seiki Co., Ltd., using instrument names MFR meter E Unit, 300 ° C., a load 1.2 kg, was measured melt flowability MVR (cm ^3/10 min).

(2) YI value Using the pellets obtained above, a plate-like molded product of 50 mm × 90 mm × thickness 5 mm was molded at a cylinder temperature of 320 ° C. and a mold temperature of 80 ° C. and a cycle time of 50 seconds. About the obtained molded object, YI value was measured on condition of C light source and a 2 degree visual field using the spectrophotometer.

(3) YI value (350 ° C., 3 minutes) and YI value (350 ° C., 10 minutes)
About the pellet obtained by the said method, the residence heat stability test was done as follows by injection molding, and the YI value of the molded article of residence time 3 minutes and 10 minutes was measured.
<injection molding>
Injection molding machine: Toshiba Machine Co., Ltd. EC40N (trade name)
Molded product shape: 80 mm x 40 mm x 3.2 mm
Molding machine cylinder temperature: 350 ° C
Residence time in cylinder: 3 minutes or 10 minutes Mold temperature: 80 ° C
(4) Bending strength A flat molded body of 50 mm × 90 mm × thickness 0.5 mm was molded at a mold temperature of 110 ° C. and a cycle time of 50 seconds with a cylinder temperature setting of 350 ° C. The obtained sample was placed on a 50 mm wide jig set at a fulcrum of 30 mm, the test was performed at a test speed of 0.5 mm / m, and the bending strength of the formed product was measured.

  From the comparison between Examples 1 to 14 and Comparative Examples 1 to 4, a resin composition comprising a polycarbonate resin produced using high-purity 3-pentadecylphenol as a terminal terminator belonging to the present invention is a conventional one. Compared to a resin composition containing a polycarbonate resin, it is understood that the fluidity is excellent, the YI value is low, the color tone and transparency are excellent, and the molding stability at high temperature is excellent.

  The polycarbonate resin composition of the present invention is excellent in fluidity, excellent in light transmittance and brightness, excellent in molding stability at high temperatures, and can be obtained in excellent light transmittance. Discoloration and deterioration do not occur even in a humid environment for a long time. Therefore, the polycarbonate resin composition of the present invention is particularly useful as an optical molded product, particularly as a light guide plate, and further as a light guide plate for a thin-walled large-screen liquid crystal display device.

Claims (14)

1% by mass or less of the resorcinol derivative represented by the following general formula (I) and / or 2.5% by mass or less of the phenol derivative represented by the following general formula (II), the total content of the resorcinol derivative and the phenol derivative 380 nm light transmission in a 3 mm-thick molded product molded at 350 ° C. using a terminal stopper containing 3-pentadecylphenol having an amount of 2.5% by mass or less and a purity of 97.5% by mass or more as a raw material Polycarbonate resin (A) comprising 10-100% by mass of polycarbonate resin (A-1) having a rate of 85.0% or more, and 90-0% by mass of polycarbonate resin (A-2) other than (A-1). For 100 parts by mass of phosphorus antioxidant (B) 0.005 to 0.5 parts by mass of alicyclic epoxy compound (C) 0.001~0. Polycarbonate resin composition containing a mass parts.

[In formula, R < ¹ >, R < ² > is a hydrogen atom or a C1-C20 aliphatic hydrocarbon group. R ³ is a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms. R ¹ , R ² and R ³ may be the same or different. However, in the above general formula (II), 3-pentadecylphenol represented by R ¹ = H and R ³ = C ₁₅ H ₃₁ is excluded. ] The polycarbonate resin composition according to claim 1 , wherein the purity of the 3-pentadecylphenol is 99.0% by mass or more. Said 3 After pentadecyl phenol distillation, obtained by performing the crystallization, polycarbonate resin composition according to claim 1 or 2. The polycarbonate resin composition in any one of Claims 1-3 whose content of 3-pentadecyl phenoxy group in the said (A) component is 0.1-10 mass%. The component (B) has a pentaerythritol structure, polycarbonate resin composition according to any one of claims 1-4. The component (B) is represented by the following formula, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, polycarbonate resin composition according to any one of claims 1-5.
The component (C), 3,4-epoxy-cyclohexylene Rumechiru -3 ', 4'-epoxy cyclohexanol down carboxylate, 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy -4 The polycarbonate resin composition according to any one of claims 1 to 6 , which is a-(2-oxiranyl) cyclohexane adduct and a mixture thereof. The polycarbonate resin composition according to any one of claims 1 to 7 , further comprising 0.02 to 0.15 parts by mass of a polyorganosiloxane (D) having a functional group with respect to 100 parts by mass of the component (A). object. The functional group is at least one alkoxy group, an aryloxy group, a polyoxyalkylene group, a carboxyl group, a silanol group, an amino group, selected from the group consisting of mercapto group, an epoxy group and a vinyl group, according to claim 8 Polycarbonate resin composition. The polycarbonate resin composition according to claim 8 or 9 , wherein a difference between a refractive index of the polyorganosiloxane (D) having the functional group and a refractive index of the polycarbonate resin (A) is 0.13 or less. The polycarbonate viscosity average molecular weight of the resin (A) is 8,000～19,000, polycarbonate resin composition according to any one of claims 1-10. Molded body obtained by molding the polycarbonate resin composition according to any one of claims 1 to 11. The molded body according to claim 12 , wherein the molded body is a light guide member. The molded body according to claim 13 , wherein the light guide member is a light guide plate.