CN106133058A - Polycarbonate resin composition and molded article - Google Patents

Abstract

The invention provides a polycarbonate resin composition which is improved in fluidity and color tone and excellent in molding stability at high temperatures, and a molded article thereof. The present invention provides (1) a polycarbonate resin composition comprising 0.005 to 0.5 parts by mass of a phosphorus antioxidant (B) per 100 parts by mass of 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 polycarbonate resin (A-1), wherein the polycarbonate resin (A-1) is produced by using an end-capping agent comprising 1% by mass or less of a resorcinol derivative and/or 2.5% by mass or less of a phenol derivative, the total content of the resorcinol derivative and the phenol derivative being 2.5% by mass or less, and further comprising 3-pentadecylphenol having a purity of 97.5% by mass or more as a raw material, and wherein a 380nm light transmittance in a molded article having a thickness of 3mm and molded at 350 ℃ is 85.0% or more, and (2) a molded article, is obtained by molding the polycarbonate resin composition.

Description

Polycarbonate resin composition and molded article

technical field

The present invention relates to a polycarbonate resin composition and a molded article, and more specifically, to a polycarbonate resin composition having improved fluidity and color tone and excellent high-temperature molding stability, as The optical molded article is useful as a light guide plate in particular, and also relates to a molded article using the polycarbonate resin composition.

Background technique

Aromatic polycarbonate resins are excellent in transparency, mechanical properties, thermal properties, electrical properties, and weather resistance, and are used in optical moldings such as light guide plates, lenses, and optical fibers by utilizing their properties. Materials for optical moldings require high light-guiding performance, so we have developed copolycarbonate resins and improved performance with various additives. In recent years, display products such as smartphones and tablet PCs, which have larger screens and are thinner than existing products, have begun to spread, and further improvements in fluidity are required for their materials.

In order to improve the fluidity of the aromatic polycarbonate resin, for example, a method of reducing the molecular weight of the aromatic polycarbonate resin has been proposed, or a method of copolymerizing poly(1,4-butylene glycol) with poly(1,4-butylene glycol) as disclosed in Patent Documents 1 and 2 has been proposed. A method for preparing a polycarbonate resin composition by combining high flow copolycarbonate resins of polyether diols. However, when the fluidity is improved by such a method, there is a problem that the moisture resistance of the molded article is lowered. In addition, if a phosphite-based antioxidant is added to the aromatic polycarbonate resin in order to cope with high-temperature molding, the phosphite-based antioxidant is easily hydrolyzed, and even after being processed into a light guide plate, the In the heat-and-moisture resistance test performed under the above temperature and humidity conditions, it hydrolyzes, and there exists a problem that the light-guiding performance of a light-guide plate falls. In addition, a light guide plate using a low-molecular-weight polycarbonate resin with improved fluidity tends to generate cracks inside the light guide plate after a heat-and-moisture test, and there is also a problem that internal defects are easily formed.

In addition, Patent Document 3 describes an optical recording medium using polycarbonate having m-pentadecylphenoxy end groups, but the color tone is not sufficiently satisfactory.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2009-298994

Patent Document 2: Japanese Patent Laid-Open No. 2009-40843

Patent Document 3: Japanese Patent Laid-Open No. 2003-41011

Contents of the invention

The problem to be solved by the invention

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 temperature, and a molded article thereof.

method used to solve the problem

The present invention relates to the following 1-15.

1. A polycarbonate resin composition comprising 10 to 100% by mass of polycarbonate resin (A-1) and 90% of polycarbonate resin (A-2) other than (A-1) ～0 mass % polycarbonate resin (A) 100 mass parts, contain phosphorus antioxidant (B) 0.005～0.5 mass part, described polycarbonate resin (A-1) uses as raw material and contains following general formula ( I) The resorcinol derivative represented by 1% by mass or less and/or the phenol derivative represented by the following general formula (II) is 2.5% by mass or less, the total content of the resorcinol derivative and the phenol derivative is 2.5% by mass or less, and a terminal blocking agent containing 3-pentadecylphenol with a purity of 97.5% by mass or more, the light transmittance at 380 nm in a molded product with a thickness of 3 mm molded at 350° C. is 85.0% or more.

[chemical 1]

In the formula, R ¹ and R ² are hydrogen atoms or aliphatic hydrocarbon groups with 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.

2. The polycarbonate resin composition as described in said 1 which further contains 0.001-0.5 mass parts of aliphatic cyclic epoxy compounds (C) with respect to 100 mass parts of said (A) components.

3. The polycarbonate resin composition according to the above 1 or 2, wherein the purity of the 3-pentadecylphenol is 99.0% by mass or more.

4. The polycarbonate resin composition according to any one of 1 to 3 above, wherein the 3-pentadecylphenol is obtained by crystallization after distillation.

5. The polycarbonate resin composition according to any one of 1 to 4 above, wherein the content of the 3-pentadecylphenoxy group in the component (A) is 0.1 to 10% by mass.

6. The polycarbonate resin composition according to any one of the above 1 to 5, wherein the component (B) has a pentaerythritol structure.

7. The polycarbonate resin composition according to any one of 1 to 6 above, wherein the component (B) is bis(2,4-dicumylphenyl)pentaerythritol represented by the following general formula: Diphosphite.

[Chem 2]

8. The polycarbonate resin composition according to any one of 2 to 7 above, wherein the component (C) is selected from the group consisting of 3,4-epoxycyclohexenylmethyl-3',4' - Epoxycyclohexene carboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, and at least one of their mixtures.

9. The polycarbonate resin composition according to any one of 1 to 8 above, which further contains 0.02 to 100 parts by mass of polyorganosiloxane (D) having a functional group with respect to 100 parts by mass of the component (A). 0.15 parts by mass.

10. According to the polycarbonate resin composition described in said 9, wherein, the functional group is selected from the group consisting of alkoxy, aryloxy, polyoxyalkylene, carboxyl, silanol, amino, mercapto, epoxy and at least one of vinyl.

11. The polycarbonate resin composition according to the above 9 or 10, wherein the refractive index of the polyorganosiloxane (D) having a functional group is equal to the refractive index of the polycarbonate resin (A). The difference is 0.13 or less.

12. The polycarbonate resin composition according to any one of 1 to 11 above, wherein the polycarbonate resin (A) has a viscosity average molecular weight of 8,000 to 19,000.

13. A molded article obtained by molding the polycarbonate resin composition described in any one of 1 to 12 above.

14. The molded article according to 13 above, wherein the molded article is a light guide member.

15. The molded article according to 14 above, wherein the light guide member is a light guide plate.

Invention effect

According to the present invention, it is possible to provide a polycarbonate resin composition having improved fluidity and color tone, and excellent molding stability at high temperature, and a molded article.

detailed description

[Polycarbonate resin composition]

The polycarbonate resin composition of the present invention contains 10 to 100% by mass of the polycarbonate resin (A-1) and 90 to 0% by mass of the polycarbonate resin (A-2) other than the above (A-1). 100 parts by mass of the polycarbonate resin (A) contains 0.005 to 0.5 parts by mass of a phosphorus-based antioxidant (B). Hereinafter, the polycarbonate resin composition of this invention is demonstrated.

〔Polycarbonate resin (A-1)〕

The polycarbonate resin (A-1) contains not more than 1% by mass of a resorcinol derivative represented by the following general formula (I) and/or not more than 2.5% by mass of a phenol derivative represented by the following general formula (II) obtained by using the total content of the resorcinol derivative and the phenol derivative at 2.5% by mass or less, and using an end-capping agent containing 3-pentadecylphenol with a purity of 97.5% by mass or more as a raw material resin.

3-Pentadecylphenol having a purity of 97.5% by mass or more to be used as an end-blocking agent of the polycarbonate resin (A-1) is preferably obtained from a natural product.

In addition, in this specification, 3-pentadecylphenol whose purity is 97.5 mass % or more may be called "high-purity 3-pentadecylphenol."

<High-purity 3-pentadecylphenol>

The purity of the high-purity 3-pentadecylphenol used in this invention needs to be 97.5 mass % or more. If the purity is less than 97.5% by mass, when used as a raw material for polymer materials such as polycarbonate resins, the degree of yellowness will be high, and the transparency and appearance may be deteriorated. From the above viewpoints, the purity of high-purity 3-pentadecylphenol is preferably 99.0% by mass or more.

In order to obtain such high-purity 3-pentadecylphenol, a natural product extract derived from the shell liquid of cashew nuts is used. It is particularly effective to use cardanol, which is contained in the shell liquid of cashew nuts at about 10% by mass, as a production raw material. Cardanol contained in the cashew nut shell liquid is mainly 3-pentadecylphenol, 3-pentadecylphenol monoene, 3-pentadecylphenol diene, and 3-pentadecylphenol diene represented by the following general formula (III). - Mixtures of pentadecylphenoltrienes.

[Chem 3]

In the above formula (III), when R ⁴ is -(CH ₂ ) ₁₄ CH ₃ , it is 3-pentadecylphenol, and when R ⁴ is -(CH ₂ ) ₇ CH=CH(CH ₂ ) ₅ In the case of _CH3 , it is ³ -pentadecylphenol monoene, and when R4 is -( _CH2 )7CH= _CHCH2CH = _CH ( _CH2 ) _CH3 , it is 3-pentadecane In the case of R ⁴ being -(CH ₂ ) ₇ CH=CHCH ₂ CH=CHCH ₂ CH=CH ₂ , it is 3-pentadecylphenol diene.

As described above, the main component of cardanol contained in the cashew nut shell liquid contains a phenol derivative having a hydrocarbon group at the 3-position (meta-position), the hydrocarbon group having a saturated bond and 1 to 3 unsaturated double bonds, and the carbon The atomic number is 15.

In order to efficiently obtain high-purity 3-pentadecylphenol with a purity of 97.5 mass % or more used in the present invention, it is preferable to use cardanol contained in cashew nut shell liquid, and it is most preferable to use the cardanol that is subjected to hydrogenation reaction treatment. A method of highly purifying the obtained crude pentadecylphenol (low-purity pentadecylphenol). In addition, a method of high-purification using crude pentadecylphenol obtained by directly hydrotreating cashew nut shell liquid and distilling the obtained hydrotreated liquid may also be employed. Moreover, commercially available pentadecylphenol is obtained by hydrogenating cardanol contained in cashew nut shell liquid, but since its purity is usually lower than 97.5% by mass, it is difficult to use commercially available pentadecylphenol In some cases, high purification is required.

<Hydrotreatment method>

In order to obtain 3-pentadecylphenol, it is preferable to hydrogenate the unsaturated bond (double bond) of the linear hydrocarbon portion of cardanol as described above to convert it to a saturated bond. In order to increase the purity of 3-pentadecylphenol in a state where the straight-chain hydrocarbon portion contains many unsaturated bonds, it may be necessary to repeatedly carry out distillation or crystallization, resulting in decreased productivity. Therefore, the conversion rate (hydrogenation rate) of unsaturated bonds by hydrogenation is preferably 90 mol% or more, more preferably 95 mol% or more. The residual ratio of unsaturated bonds in cardanol after hydrogenation (the number of unsaturated bonds per molecule of cardanol) is preferably 0.2 or less per molecule, more preferably 0.1 or less.

The hydrogenation method is not particularly limited, and a usual method can be used. Examples of the catalyst include noble metals such as palladium, ruthenium, rhodium, and platinum, nickel, or metals selected from these supported on supports such as activated carbon, activated alumina, and diatomaceous earth. As the reaction method, a batch method in which the reaction is carried out while suspending and stirring the powdery catalyst, or a continuous method using a reaction tower filled with a molded catalyst can be employed. Depending on the method of hydrogenation, a solvent for hydrogenation may not be used, and when a solvent is used, alcohols, ethers, esters, and saturated hydrocarbons are generally used. The reaction temperature during hydrogenation is not particularly limited, but usually can be set to 20 to 250°C, preferably 50 to 200°C. If the reaction temperature is too low, the hydrogenation rate will slow down, and conversely, if it is too high, the decomposition products will tend to increase. The hydrogen pressure during hydrogenation can be usually set to 80kgf/cm ² (atmospheric pressure to 78.4×10 ⁵ Pa), preferably 3 to 50kgf/cm ² (2.9×10 ⁵ to 49.0×10 ⁵ Pa) .

<High Purification Method>

The purity of crude pentadecylphenol (low-purity pentadecylphenol) obtained by the above-mentioned hydrotreatment method is usually 90 to 93% by mass, and contains various resorcinol derivatives or 3-pentadecane as impurities. Phenol derivatives other than phenols.

In addition, in this specification, a resorcinol derivative is a compound having a structure having two OR groups (R represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.) at the meta-position of the benzene ring. , The so-called phenol derivatives are compounds having a structure having one OR group in the benzene ring.

As a method of obtaining high-purity 3-pentadecylphenol with a purity of 97.5% by mass or more used in the present invention, there is mentioned the high-purification of crude pentadecylphenol obtained by the aforementioned hydrotreatment method by distillation. method, a method of high purification by crystallization, a method of high purification by crystallization after distillation, etc. Among these methods, a method in which crude pentadecylphenol is distilled and then crystallized is preferred. In addition, 3-pentadecylphenol having a high purity of 97.5% by mass or more can be used, and further distillation and crystallization can be repeated to obtain 3-pentadecylphenol with higher purity.

As a method of high-purification by distillation, for example, high-purification by atmospheric distillation or vacuum distillation can be used, and high-purification by vacuum distillation is preferable among them. When performing high-purification by vacuum distillation, it is preferable to set the main fraction at a temperature of 200 to 260° C. and a pressure of 1 to 10 mmHg, and to use a filler in the vacuum distillation column for treatment. At this time, it is preferable to set the reflux ratio (reflux Flow rate/distillation amount) was set to 0.5-10. As the filler used in the vacuum distillation column, fillers such as McMahon packing, Dixon packing, Raschig rings, Pall rings, ring packings, and Hillie Packing can be used, but McMahon packing is preferably used.

As a method for highly purifying 3-pentadecylphenol by crystallization, the temperature of a solution in which crude pentadecylphenol is dissolved in a crystallization solvent can be lowered in a crystallization tank, and the crystallization method can be used to obtain high-purity. The difference between the supersaturated state of the 3-pentadecylphenol solution and the saturation concentration of the compound makes the 3-pentadecylphenol precipitate and generate the crystal of 3-pentadecylphenol, and then the 3-pentadecylphenol in the crystal state -Pentadecylphenol is separated from the solid and liquid in the solution, whereby high-purity 3-pentadecylphenol can be obtained. The crystallization operation can be carried out 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 them, hydrocarbon-based solvents are preferable, and hexane and heptane are more preferable. The amount of the crystallization solvent used can be appropriately set, but it is preferably 2 to 20 parts by mass, more preferably 4 to 10 parts by mass, of the crystallization solvent relative to 1 part by mass of 3-pentadecylphenol. Produce efficiently while ensuring desired purity. In addition, although the crystallization can be performed without adding a seed crystal, the crystallization can be efficiently performed by adding a seed crystal.

In addition, when the temperature of the solution in which the crude pentadecylphenol is dissolved in the crystallization solvent is lowered in the crystallization tank, a controlled cooling method, a linear cooling method, a natural cooling method, etc. are known, but the cooling method is not particularly limited. , and the cooling rate can be set appropriately. Among them, the controlled cooling method reduces the temperature change (slows down the cooling rate) at the initial stage when the crystallization amount is small, and increases the temperature change (speeds up the cooling rate) at the end stage when the crystallization amount increases, thereby keeping the supersaturation of the saturated solution low. Since the ground is kept constant, the generation of secondary nuclei is suppressed, and only monodisperse particles can be obtained, which is preferable. The cooling rate is preferably set at 0°C (constant temperature) to -10°C/h at the initial stage, more preferably at 0°C (constant temperature) to -5°C/h, and at the end stage it is preferable to perform high purification The temperature is lowered at -5°C/h to -30°C/h, more preferably at -10°C to -20°C/h.

By the high-purification method described above, 3-pentadecylphenol having a purity of 97.5% by mass or higher can be obtained from crude pentadecylphenol.

In the high-purity 3-pentadecylphenol used in the present invention, it is required to contain not more than 1% by mass of a resorcinol derivative represented by the following general formula (I) and/or a resorcinol derivative represented by the following general formula (II) The phenol derivative is 2.5% 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, it is preferable that 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. mass % or less, and the total amount of the resorcinol derivative and the phenol derivative is 0.8 mass % or less.

[chemical 4]

In the above 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, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and other alkyl groups. With respect to R ³ being a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, in addition to the alkyl groups exemplified for R ¹ and R ² above, one or more A carbon-carbon unsaturated double bond monoene, diene, triene unsaturated aliphatic hydrocarbon group.

For the compound contained in the above-mentioned general formula (I), examples of compounds in which both R ¹ and R ² are hydrogen atoms include 5-pentadecylresorcinol, 5-methylresorcinol, 5-methylresorcinol, -Ethylresorcinol, 5-propylresorcinol, 5-butylresorcinol, 5-hexylresorcinol, 5-octylresorcinol, 5-decylresorcinol R ³ is carbon A compound of an alkyl group with 1 to 20 atoms, in addition, in the alkyl group, it may also be an unsaturated aliphatic group such as a monoene, a diene, a triene, etc., having one or more carbon-carbon unsaturated double bonds. Hydrocarbyl.

In addition, in the above general formula (I), as 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 aliphatic hydrocarbon group having 1 to 20 carbon atoms Compounds, for example, 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 Alkylphenol, 3-methoxy-5-nonadecylphenol, 3-ethoxy-5-hexylphenol, 3-ethoxy-5-octylphenol, 3-ethoxy-5-decylphenol 3-ethoxy-5-dodecylphenol, 3-ethoxy-5-tetradecylphenol, 3-ethoxy-5-heptadecylphenol, 3-ethoxy - Compounds such as 5-octadecylphenol, 3-ethoxy-5-nonadecylphenol, etc. In addition, in the 5-position alkyl group, there may be one or more than one carbon-carbon Unsaturated aliphatic hydrocarbon groups such as monoene, diene, and triene with saturated double bonds.

For the compound contained in the above-mentioned general formula (II), as a compound wherein R ¹ is a hydrogen atom and R ³ is a saturated or unsaturated aliphatic hydrocarbon group with 1 to 20 carbon atoms, 3-hexylphenol, 3 -Octylphenol, 3-decylphenol, 3-dodecylphenol, 3-tridecylphenol, 3-tetradecylphenol, 3-hexadecylphenol, 3-octadecylphenol , 3-nonadecylphenol and other compounds having an alkyl group at the 3-position, or monoene, diene, triene and other unsaturated compounds having one or more carbon-carbon unsaturated double bonds in the alkyl group Aliphatic hydrocarbon group.

In addition, as a compound in which R1 is an aliphatic hydrocarbon group having ¹ to 20 carbon atoms, for example, when the 3-position is a hexyl group, 1-methoxy-3-hexylbenzene, 1-ethoxy-3 -Hexylbenzene, 1-propoxy-3-hexylbenzene, 1-butoxy-3-hexylbenzene, 1-pentyloxy-3-hexylbenzene, 1-hexyloxy-3-hexylbenzene, 1- Compounds such as octyloxy-3-hexylbenzene, 1-decyloxy-3-hexylbenzene, 1-dodecyloxy-3-hexylbenzene, and 1-tetradecyloxy-3-hexylbenzene. When the 3-position is pentadecyl, examples include 1-methoxy-3-pentadecylbenzene, 1-ethoxy-3-pentadecylbenzene, 1-propoxy-3 -pentadecylbenzene, 1-butoxy-3-pentadecylbenzene, 1-pentyloxy-3-pentadecylbenzene, 1-hexyloxy-3-pentadecylbenzene, 1 -Octyloxy-3-pentadecylbenzene, 1-decyloxy-3-pentadecylbenzene, 1-dodecyloxy-3-pentadecylbenzene, 1-tetradecyloxy -3-pentadecylbenzene and other compounds.

In addition, in the general formula (I) and general formula (II), the illustrated alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group.

<Polycarbonate resin (A-1)>

The polycarbonate resin (A-1) is preferably an aromatic polycarbonate resin whose main chain contains a repeating unit represented by the following general formula (IV).

The polycarbonate resin (A-1) may be used alone or in combination of two or more.

[chemical 5]

In the formula, R ⁵ and R ⁶ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group with 1 to 8 carbon atoms, an alkylidene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 15 carbon atoms, and a cycloalkylidene group with 5 to 15 carbon atoms , fluorenediyl, arylalkylene with 7 to 15 carbon atoms, arylalkylidene with 7 to 15 carbon atoms, -S-, -SO-, -SO ₂ -, -O- or -CO -. a and b each independently represent an integer of 0-4.

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.

^The alkyl groups independently represented by ^R5 and R6 include methyl, ethyl, n-propyl, isopropyl, and various butyl groups (the so-called "various" includes straight chains and all branched chains) Like groups, the same below.), various pentyl groups, various hexyl groups. Examples of the alkoxy group independently represented by R ⁵ and R ⁶ include the case where the alkyl moiety is the above-mentioned alkyl group.

Both R ⁵ and R ⁶ are preferably 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 1,3-propylene group, a 1,4-butylene group, a 1,6-hexylene group, etc., and the number of carbon atoms is preferably 1 to 5 alkylene groups. Examples of the alkylidene group represented by X include an ethylidene group, an isopropylidene group, and the like. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, a cyclooctanediyl group, and the like, preferably a cycloalkylene group having 5 to 10 carbon atoms. The cycloalkylidene group represented by X includes, for example, cyclohexylidene group, 3,5,5-trimethylcyclohexylidene group, 2-adamantylidene group, etc., preferably a ring having 5 to 10 carbon atoms. The alkylidene group is more preferably a cycloalkylidene group having 5 to 8 carbon atoms.

Examples of the aryl portion of the arylalkylene group represented by X and the aryl portion of the arylalkylidene group represented by X include ring-forming carbon atoms such as phenyl, naphthyl, biphenyl, and anthracenyl. The aryl group whose number is 6-14.

a and b each independently represent an integer of 0-4, preferably 0-2, and more preferably 0 or 1.

<Manufacturing method of 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 above-mentioned high-purity 3-pentadecylphenol as a terminal group as a terminal blocking agent.

As the blocking agent, a blocking agent other than high-purity 3-pentadecylphenol (other blocking agents) may be used in combination with high-purity 3-pentadecylphenol. As other end-blocking agents, conventionally used end-blocking agents for producing polycarbonate resins can be used, for example, phenol, p-cresol, p-tert-butylphenol, p-cumylphenol, tribromophenol, nonyl Phenol, p-tert-octylphenol, etc. Among them, p-tert-butylphenol and p-cumylphenol are preferable. When high-purity 3-pentadecylphenol is used together with other blocking agents, the molar ratio of (3-pentadecylphenol):(other blocking agents) is preferably 99:1. ~ 20:80, more preferably 90:10 ~ 30:70.

In order to manufacture a polycarbonate resin (A-1), it is necessary to use the dihydric phenol which comprises a main chain. As the dihydric phenol, various known dihydric phenols can be used, but the dihydric phenol represented by the following general formula (1) is preferably used.

[chemical 6]

Here, in the above general formula (1), R ⁵ , R ⁶ , X, a, and b are the same as described 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 suitable.

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-tert-butylphenyl)propane, 2,2-bis(4 -Hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane , 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane and other bis(hydroxyaryl)alkanes Classes, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5 , 5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornane, 1,1-bis(4-hydroxyphenyl)cyclododecane and other bis(hydroxyaryl) rings Alkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether and other dihydroxyaryl ethers, 4,4'-dihydroxydiphenyl ether Phenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide and other dihydroxy diaryl sulfides, 4,4'-dihydroxy diphenyl sulfoxide, 4 , 4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide and other dihydroxydiarylsulfoxides, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy- Dihydroxydiarylsulfones such as 3,3'-dimethyldiphenylsulfone, dihydroxybiphenyls such as 4,4'-dihydroxybiphenyl, 9,9-bis(4-hydroxyphenyl)fluorene , 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and other dihydroxydiaryl fluorenes, 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4 -Hydroxyphenyl)adamantane, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane and other dihydroxydiaryladamantanes, 4,4'-[1,3- Phenylenebis(1-methylethylidene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-anthrone, 1,5-bis(4-hydroxyphenylthio)-2 , 3-dioxapentane, etc.

These dihydric phenols may be used alone or in combination of two or more.

In addition, as the dihydric phenol not contained in the dihydric phenol represented by the general formula (1) above, a dihydric phenol containing a structural unit represented by the following general formula (2) can be combined with a dihydric phenol represented by the above general formula (1) The indicated dihydric phenols are used in combination. By forming a copolymer having such a structural unit, the flame retardancy and impact resistance of the obtained polycarbonate resin (A-1) can be improved. The dihydric phenol containing the structural unit represented by following general formula (2) can be represented by the polyorganosiloxane represented by following general formula (2-1).

[chemical 7]

In the above general formula (2) or general formula (2-1), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. An alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Z represents a phenol residue having a 1,3-propylene group derived from a phenol compound having an allyl group. n represents 70-1000.

The polyorganosiloxane represented by the above-mentioned general formula (2-1) is a polyorganosiloxane having a hydrogen terminal at the terminal thereof with a phenol having an allyl group at the terminal such as 2-allylphenol and eugenol. Substances obtained by modifying compounds. 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 said polyorganosiloxane, polydimethylsiloxane is suitable.

In addition, a branching agent may be used for the above-mentioned dihydric phenol to have a branched chain structure in the main chain of the polycarbonate resin. The amount of the branching agent added is preferably 0.01 to 3 mol%, more preferably 0.1 to 1.0 mol%, based on the aforementioned dihydric phenol.

Examples of branching agents include 1,1,1-tris(4-hydroxyphenyl)ethane, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1- Methylethyl]phenyl]ethylidene]bisphenol, α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, 1-[α-methyl Base-α-(4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(4"-hydroxyphenyl)ethyl]benzene, phloroglucinol, trimellitic acid, indigo A compound having three or more functional groups, such as red xylenol.

The polycarbonate resin (A-1) can be produced by reacting a carbonate raw material with dihydric phenol. The carbonate raw material is a compound that can form a carbonate bond in a polycarbonate main chain by a polymer formation reaction such as a condensation reaction or an exchange reaction. As such compounds, in the case of producing polycarbonate by the interfacial polycondensation method, tricarbonyl chloride, bromocarbonyl chloride, bis(2,4,6-trichlorophenyl)carbonate, Phosgene derivatives such as bis(2,4-dichlorophenyl)carbonate, bis(2-cyanophenyl)carbonate, and trichloromethyl chloroformate.

In addition, in the production of polycarbonate by the transesterification method (melt method), a carbonic acid diester is used as a carbonate raw material, and the carbonic acid diester includes a diaryl carbonate compound, a dialkyl carbonate compound, and a carbonic acid diester. , alkyl aryl carbonate compounds, etc.

Here, as specific examples of the diaryl carbonate compound, diphenyl carbonate, xylyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis( Diphenyl) carbonate, bisphenol A diphenyl carbonate, and the like. Specific examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A dimethyl carbonate, and the like. Specific examples of alkyl aryl carbonate compounds include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A methyl phenyl Carbonate etc.

The polycarbonate resin (A-1) can be produced by a method commonly used in the production of common polycarbonate resins, such as an interfacial polycondensation method using phosgene or a phosgene derivative, and a transesterification method (melt method). Among them, the interfacial polycondensation method is preferable.

As an interfacial polycondensation method using phosgene or a phosgene derivative, for example, a polycarbonate oligomer of the dihydric phenol synthesized in advance from the above-mentioned dihydric phenol and phosgene or a phosgene derivative, and adding to the polycarbonate oligomer A method in which an aqueous alkali solution containing the dihydric phenol and an end-capping agent containing the high-purity 3-pentadecylphenol is added to the inert organic solvent solution of the oligomer to react; or to the dihydric phenol Alkali aqueous solution, the method of adding carbonyl chloride or carbonyl chloride derivatives to the mixed solution containing the high-purity 3-pentadecylphenol end-capping agent and an inert organic solvent to make it react, etc., and among them, suitable for The former oligomer method.

Next, a method for producing 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 to prepare an alkaline aqueous solution of the dihydric phenol ( aqueous solution of sodium hydroxide, etc.). Then, phosgene or a phosgene derivative is introduced into a mixture of the alkali aqueous solution and an inert organic solvent (organic solvent such as methylene chloride) to synthesize a polycarbonate oligomer of the dihydric phenol. In this case, 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. The reaction temperature is cooled in a water bath, usually in the range of 0 to 50°C, preferably 5 to 40°C, and the reaction time is usually 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 2-10.

Here, to the thus-obtained organic phase containing polycarbonate oligomers, add the alkaline aqueous solution of the dihydric phenol, the end-capping agent containing the high-purity 3-pentadecylphenol, and add They are brought into contact with an inert organic solvent by stirring or the like, and the interfacial polycondensation is usually carried out at a temperature in the range of 0 to 50°C, preferably 5 to 40°C, for about 10 minutes to 6 hours. In this case, 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. In addition, 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 Choose from 0.45 to 0.5. In addition, the ratio of the alkali metal hydroxide to the polycarbonate oligomer is such that the molar ratio of (alkali metal hydroxide)/(chloroformate group of the polycarbonate oligomer) is usually 1.0 to 2.0 , preferably in the mode of 1.2 to 1.7. Moreover, the usage-amount of a terminal blocking agent is selected so that the molar ratio of (blocking agent)/(chloroformate group of a polycarbonate oligomer) may be 0.02-0.20 normally, Preferably it is 0.04-0.17. Also, in this reaction, a catalyst may be used as required. The amount of catalyst used is such that the molar ratio of (catalyst)/(chloroformate group of polycarbonate oligomer) is usually 1.0×10 ^-3 to 10.0×10 ^-3 , preferably 1.0×10 ^-3 ~5.0×10 ^-3 mode selection.

As the hydroxide of the alkali metal used for manufacture of polycarbonate resin (A-1), sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide etc. are mentioned, for example. Among them, sodium hydroxide and potassium hydroxide are preferable. In addition, there are various solvents as the inert organic solvent. Examples include dichloromethane; chloroform; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; Ethane; 1,1,1,2-tetrachloroethane; 1,1,2,2-tetrachloroethane; pentachloroethane, chlorinated hydrocarbons such as chlorobenzene, or acetophenone, etc. These organic solvents may be used alone or in combination of two or more. Among them, chloroform and dichloromethane are preferable, and dichloromethane is particularly preferable.

As the catalyst, various catalysts can be used. Specifically, quaternary ammonium salt, quaternary phosphonium salt, tertiary amine, etc. are mentioned. As the quaternary ammonium salt, for example, trimethyl benzyl ammonium chloride, triethyl benzyl ammonium chloride, tributyl benzyl ammonium chloride, trioctyl methyl ammonium chloride, tetrabutyl benzyl ammonium chloride, Ammonium, tetrabutylammonium bromide, etc. In addition, examples of quaternary phosphonium salts include tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, etc., and examples of tertiary amines include triethylamine, tributylamine, N,N-dimethyl Cyclohexylamine, pyridine, dimethylaniline, etc.

Among the catalysts, preference is given to tertiary amines, particular preference to triethylamine. The polycarbonate resin (A-1) can be obtained by recovering from the organic solvent solution containing the polycarbonate resin thus obtained according to a normal method.

In the production of polycarbonate resin based on the transesterification method (melt method), dihydric phenol, carbonic diester, and an end-capping agent containing the high-purity 3-pentadecylphenol, and if necessary branching agent, etc., in a molten state to undergo transesterification reaction, and the by-produced phenol is removed from the system under reduced pressure or the like, thereby obtaining a polycarbonate resin (A-1). In the transesterification method, a transesterification catalyst for promoting the reaction can also be used. 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 by using high-purity 3-pentadecylphenol as a terminal blocking agent, and has a terminal group derived from 3-pentadecylphenol.

The light transmittance at 380 nm of a molded article having a thickness of 3 mm obtained by molding the polycarbonate resin (A-1) at 350° C. was 85.0% or more. If the light transmittance at 380 nm is 85.0% or more, it can be applied to a light guide member for liquid crystal requiring transparency and a light guide member for liquid crystal with a thin wall and a large screen. From the above viewpoints, the 380 nm light transmittance is preferably 86% or higher, more preferably 87% or higher.

The viscosity average molecular weight of the polycarbonate resin (A-1) is not particularly limited, but it is preferably 8,000 to 19,000, more preferably 9,000 to 17,000, more preferably 10,000 to 15,000.

The polycarbonate resin (A-1) preferably has a yellow index (YI) of 1.5 or less. When YI of a polycarbonate resin (A-1) is 1.5 or less, it can be used suitably for the member for liquid crystals which are excellent in color tone and require transparency. From the above viewpoints, 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 this invention may contain polycarbonate resin (A-2) other than polycarbonate resin (A-1).

As the polycarbonate resin (A-2), various known polycarbonate resins can be used without particular limitation, however, an aromatic polycarbonate resin is preferable.

The viscosity average molecular weight of the polycarbonate resin of this (A-2) component is preferably 10,000 to 40,000, more preferably 11,000 to 17,000 from the viewpoint of physical properties.

The above-mentioned aromatic polycarbonate resin is preferably a resin containing a repeating unit represented by the following general formula (V) in the main chain.

[chemical 8]

In the formula, R ⁹ and R ¹⁰ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X' represents a single bond, an alkylene group with 1 to 8 carbon atoms, an alkylidene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 15 carbon atoms, and a cycloalkylidene group with 5 to 15 carbon atoms group, -S-, -SO-, -SO ₂ -, -O- or -CO-. d and e each independently represent the integer of 0-4.

Specific examples of R ⁹ and R ¹⁰ include the same examples as those for R ⁵ and R ⁶ described above. 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 examples as X described above, and preferred examples are also the same. d and e are each independently, preferably 0-2, more preferably 0 or 1.

Specifically, as the aromatic polycarbonate resin, a resin obtained by a conventional method for producing an aromatic polycarbonate by mixing an aromatic polycarbonate with an aromatic polycarbonate in the presence of an inert organic solvent or an aqueous alkali solution can be used. The interfacial polymerization method in which the aromatic dihydric phenolic compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent by adding a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt after the reaction of the aromatic dihydric phenolic compound and phosgene Among them, the pyridine method of direct production by introducing carbonyl chloride.

In the above-mentioned reaction, a molecular weight regulator (end-capping agent), a branching agent, and the like can be used as necessary.

Moreover, the compound represented by following general formula (3) is mentioned as said aromatic dihydric phenol type compound.

[chemical 9]

In the formula, R ⁹ , R ¹⁰ , X', d and e are as defined above, and preferred examples are also the same.

Specific examples of the aromatic dihydric phenol compound include the same examples as those of the dihydric phenol represented by the general formula (1), and preferred examples are also the same. In addition, as the dihydric phenol not contained in the dihydric phenol represented by the above-mentioned general formula (3), the dihydric phenol containing the structural unit represented by the above-mentioned general formula (2) can be obtained by the above-mentioned general formula ( The polyorganosiloxane represented by 2-1) is used in combination with the dihydric phenol represented by the general formula (3).

The said dihydric 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 in the same manner.

As the terminal blocking agent, conventionally used terminal blocking agents for producing polycarbonate resins can be used, for example, phenol, p-cresol, p-tert-butylphenol, p-cumylphenol, tribromophenol, nonylphenol , p-tert-octylphenol, etc. Among them, p-tert-butylphenol and p-cumylphenol are preferable.

〔Polycarbonate resin (A)〕

The polycarbonate resin (A) contains 10-100 mass % of the said polycarbonate resin (A-1), and 90-0 mass % of the said polycarbonate resin (A-2).

The content of the polycarbonate resin (A-1) in the component (A) is 10 to 100% by mass, preferably 30 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass %.

When the polycarbonate resin composition of the present invention contains a polycarbonate-based resin (A-2) other than the above-mentioned component (A-1), its content is 90% by mass or less in the component (A), preferably It is 70 mass % or less, More preferably, it is 50 mass % or less, More preferably, it is 30 mass % or less.

The content of the 3-pentadecylphenoxy group in the component (A) is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, even more preferably 0.8 to 7% by mass. (A) When content of the 3-pentadecylphenoxy group in a component is the said range, fluidity|liquidity improves, color tone improves, and durability improves.

The viscosity average molecular weight of the polycarbonate resin (A) is not particularly limited, but it is preferably 8,000 to 19,000, more preferably 9,000 to 17,000 from the viewpoint of ensuring fluidity and strength when molding a thin-walled molded product, More preferably, it is 10,000-15,000.

〔Phosphorus antioxidant (B)〕

The polycarbonate resin composition of this invention contains phosphorus antioxidant (B). By containing the phosphorus-based antioxidant (B), the increase in the YI value of the polycarbonate resin composition can be suppressed, and even if the resin composition is allowed to remain at a high temperature during molding processing, a good color tone can be maintained, and the polycarbonate resin composition can be stabilized. The carbonate resin composition imparts excellent processing stability.

As the phosphorus antioxidant, phosphorous acid, phosphonous acid, phosphonic acid, their esters, tertiary phosphine, and the like can be used. Among them, an antioxidant having a pentaerythritol structure is preferable, and a phosphite having a pentaerythritol structure represented by the following general formula (4) is more preferable.

[chemical 10]

In the general formula (4), R ⁷ and R ⁸ each represent hydrogen, an alkyl group, a cycloalkyl group or an aryl group. Furthermore, a cycloalkyl group and an 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).

[chemical 11]

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

[chemical 12]

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

[chemical 13]

As the phosphite having the pentaerythritol structure represented by the general formula (4), specifically, bis(2,6-di-tert-butyl-4-methyl) of the following general formula (5) can be exemplified. In addition to phenyl) pentaerythritol diphosphite and bis(2,4-dicumylphenyl) pentaerythritol diphosphite of the following general formula (6), the following general formulas (7) to (10 )compound of.

[chemical 14]

Among them, as the phosphorus antioxidant (B), the bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite of the general formula (5) [such as Adekastab PEP-36 : manufactured by ADEKA Co., Ltd.], bis(2,4-dicumylphenyl) pentaerythritol diphosphite of the general formula (6) [for example, Doverphos S-9228PC: manufactured by Dover Chemical Corporation], more preferably The bis(2,4-dicumylphenyl)pentaerythritol diphosphite of the general formula (6).

The content of the phosphorus-based antioxidant (B) in the polycarbonate resin composition of the present invention is 0.005 to 0.5 parts by mass, preferably 0.01 to 0.2 parts by mass, more preferably 0.02 to 0.1 parts by mass relative to 100 parts by mass of component (A). parts by mass. If it is less than 0.005 parts by mass, a rise in the YI value cannot be suppressed, and a good color tone cannot be maintained if the resin composition is left at a high temperature during molding processing. On the other hand, if it exceeds 0.5 parts by mass, hydrolysis of polycarbonate due to decomposition products will be promoted, and desired performance cannot be exhibited.

[Aliphatic Cyclic Epoxy Compound (C)]

The polycarbonate resin composition of this invention may 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 was epoxidized. By containing the aliphatic cyclic epoxy compound (C) in the polycarbonate resin composition of this invention, the durability of a molded object can be improved.

Among such aliphatic cyclic epoxy compounds (C), it is preferably selected from 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate (Daicel Chemical Industry Addition of 1,2-epoxy-4-(2-oxiranyl)cyclohexane to 2,2-bis(hydroxymethyl)-1-butanol (trade name "CELLOXIDE 2021P" manufactured by the company, etc.) (trade name "EHPE3150" manufactured by Daicel Chemical Industry Co., Ltd.) and a mixture of these two types (trade name EHPE3150CE manufactured by Daicel Chemical Industry Co., Ltd.).

It is preferable that content of the aliphatic cyclic epoxy compound (C) in the polycarbonate resin composition of this invention is 0.001-0.5 mass parts with respect to 100 mass parts of (A) components. When the said content is 0.001 mass part or more, durability improves sufficiently, and when it is 0.5 mass part or less, cloudiness can be suppressed, and a color tone will become favorable. From the above viewpoints, 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 (D) having a functional group]

The polycarbonate resin composition of this invention may contain the polyorganosiloxane (D) which has a functional group as needed.

The polyorganosiloxane having a functional group preferably has at least one functional group selected from the group consisting of alkoxy, aryloxy, polyoxyalkylene, carboxyl, silanol, amino, mercapto, epoxy and vinyl.

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

Regarding the refractive index of the above-mentioned polyorganosiloxane (D) having a functional group, in order not to reduce the transparency of the polycarbonate resin composition of the present invention, the smaller the difference in refractive index from the polycarbonate resin (A), the better. it is good. From the above viewpoints, the difference between the refractive index of the functional group-containing polyorganosiloxane (D) and the polycarbonate resin (A) is preferably 0.13 or less, more preferably 0.08 or less, and still more preferably 0.13 or less. Below 0.05. In addition, since the polycarbonate resin has a refractive index of approximately 1.58, the functional group-containing polyorganosiloxane (D) has a refractive index of preferably 1.45 or higher, more preferably 1.50 or higher, and still more preferably 1.51 or higher.

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 0.03 to 0.12 parts by mass relative to 100 parts by mass of the polycarbonate resin (A). parts by mass. When content of (D)component is mix|blended in the said range, mold releasability can be improved with other components. In addition, under high-temperature forming conditions significantly exceeding 300°C, especially under continuous forming conditions, the generation of silver (silver) and mold deposits can be greatly reduced.

[Polycarbonate resin composition/molded article]

In the polycarbonate resin composition of the present invention, in addition to the above-mentioned (A) component and (B) component, and the above-mentioned (C) component and (D) component added as needed, it can also be added without damaging Within the scope of the effects of the present invention, various known additives conventionally added to polycarbonate resin compositions may be blended as necessary.

Examples of these additives include antioxidants other than phosphorus-based antioxidants, ultraviolet absorbers, flame retardants, release agents, inorganic fillers (glass fibers, talc, titanium oxide, mica, etc.), colorants, and light diffusing agents. Wait.

The molded article composed of the polycarbonate-based resin composition of the present invention can be obtained by molding a material obtained by mixing and kneading the above-mentioned components.

The kneading method is not particularly limited, and examples include using a ribbon mixer, a Henschel mixer, a Banbury mixer, a drum mixer, a single-screw extruder, a twin-screw extruder, compounding Methods of kinematic kneaders, multi-screw extruders, etc. Moreover, the heating temperature at the time of kneading is normally 240-330 degreeC, Preferably it is selected in the range of 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 Wait.

Furthermore, components other than polycarbonate resin may be melt-kneaded with polycarbonate resin or other thermoplastic resins in advance, that is, may be added as a masterbatch.

In addition, it is preferably pelletized and injection-molded, and special molding methods such as general injection molding, injection compression molding, and gas-assisted molding can be used, and various molded products can be produced.

A molded article obtained 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. Examples of light guide members include light guide members for liquid crystal equipment such as light guide plates for liquid crystal display devices used in mobile phones, liquid crystal televisions, personal computers, electronic dictionaries, e-books, smartphones, and tablet PCs, and attached to headlights. A light guide member used in daytime running lights or LED lighting. The polycarbonate resin composition of the present invention has excellent fluidity, so when producing a particularly thin molded article, it is preferably molded by injection molding, and can be used as a resin for a light guide plate or a light diffusion plate of a liquid crystal display device Appropriately used.

Example

Examples are given below to describe the present invention in more detail. Also, the present invention is not limited by these examples. In addition, the measurement evaluation in the Example and the comparative example was performed by the method shown below.

<Methods for measuring the purity and amount of impurities of 3-pentadecylphenol>

Using "AGILENT1200" manufactured by Agilent Technologies, "L-column ODS" (4.6mmID x 150mm, particle size 3μm) was used as the column, and acetonitrile/formic acid buffer = 95/5 (vol/vol) was used as the mobile phase to measure 3- Pentadecylphenol, and resorcinol derivatives.

The phenol derivative was measured using "JMS-Q1000GC" manufactured by JEOL Ltd., using a column "VF-1" having a length of 30 m x an inner diameter of 250 μm x a film thickness of 0.25 μm.

<Measurement of Viscosity Number (VN)>

The viscosity number (VN) of the polycarbonate resin (A) was measured according to ISO1628-4 (1999).

<Measurement of Viscosity Average Molecular Weight (Mv)>

The viscosity-average molecular weight (Mv) of the polycarbonate resin (A) was calculated by the following formula by measuring the viscosity of a dichloromethane solution at 20° C. using an Ubbelohde viscometer, obtaining the intrinsic viscosity [η] from the viscosity.

[η]=1.23×10 ^-5 Mv ^0.83

<Measurement of light transmittance>

To 100 parts by mass of the obtained polycarbonate resin (A-1), add Adekastab PEP36 [manufactured by ADEKA Co., Ltd., bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite] Add 500 mass ppm, melt knead and extrude with a 40mmφ single-screw extruder with a vent at a resin temperature of 280°C and a screw speed of 100rpm to obtain pellets, and use the obtained pellets to perform injection molding at a barrel temperature of 350°C , The light transmittance at 380 nm of the obtained molded body having a thickness of 3 mm was measured with a U-4100 spectrophotometer manufactured by Hitachi High-Tech Co., Ltd. The standard of acceptance is that the transmittance at 380 nm is 85% or more.

<Measurement of terminal group composition>

Using "JNM-LA500" manufactured by JEOL Ltd., ¹ H-NMR was measured, and the terminal group composition amount of the polycarbonate resin was calculated. In addition, the content (% by mass) of the 3-pentadecylphenoxy group in the polycarbonate resin was calculated from the composition amount of terminal groups.

Preparation Example 1

A column with an inner diameter of 30mm and a capacity of 500mL is filled with McMahon packing (Mc.MAHON Packing, size: 6mm) to form a rectification column, installed in a 2L flask with an internal temperature measuring device, and installed on the top of the packed column A device for adjusting the reflux ratio (return flow/distillation flow) and a device for measuring the temperature at the top of the tower, and a device for adjusting the degree of decompression is also installed. 1006.96 g of 3-pentadecylphenol (manufactured by Tokyo Chemical Industry Co., Ltd., purity 92.10% by mass, resorcinol derivative: 2.15% by mass, 5.11% by mass of phenol derivative) was supplied to the flask, and after nitrogen replacement, the Heating and decompression. Set the degree of reduced pressure to 2 mmHg, reflux/distillation volume = 1, and separate and collect fractions with a tower top temperature of 205 to 210°C. At this time, the temperature of the flask was 230-245°C. The isolated and collected amount was 825.71 g (82% by mass of the feed), and the purity of 3-pentadecylphenol was 93.61% by mass.

Then, the obtained crude 3-pentadecylphenol was melt|dissolved in the water bath of 60 degreeC, 70g was weighed in the standard bottle, and 420g of n-hexane was added and dissolved. After standing still at room temperature for 12 hours, the precipitated solid was filtered under reduced pressure, and then dried under reduced pressure at room temperature for 8 hours to obtain 48 g of the corresponding 3-pentadecylphenol. The 3-pentadecylphenol content rate in the obtained 3-pentadecylphenol was 97.75 mass %. 70 g of the obtained 3-pentadecylphenol with a purity of 97.75% by mass was melted in a 60° C. water bath, and 70 g was weighed in a standard bottle, then 420 g of n-hexane was added and dissolved. After standing still at room temperature for 12 hours, the precipitated solid was filtered under reduced pressure, and then dried under reduced pressure at room temperature for 8 hours to obtain 54 g of 3-pentadecylphenol with a purity of 99.33% by mass. The content of the resorcinol derivative in the obtained 3-pentadecylphenol was 0.23% by mass, and the content of the phenol derivative was 0.02% by mass.

Manufacturing example 1

〔Manufacture of polycarbonate resin (A-1)〕

(1) Manufacture of polycarbonate oligomers

To an aqueous sodium hydroxide solution having a concentration of 5.6% by mass, 0.2% by mass of sodium dithionite was added to bisphenol A (BPA) dissolved thereafter, and BPA was dissolved therein so that the concentration of BPA became 13.5% by mass to prepare Sodium hydroxide solution of BPA in water. In a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m, the aqueous sodium hydroxide solution of the above-mentioned BPA was continuously fed with a flow rate of 40 L/hr, and dichloromethane was continuously fed with a flow rate of 15 L/hr, and dichloromethane was continuously fed with a flow rate of 4.0 The flow rate of kg/hr is continuously fed into phosgene. The tubular reactor has a jacket portion, and cooling water is passed through the jacket to keep the temperature of the reaction liquid below 40°C.

The reaction liquid sent from the tubular reactor is continuously introduced into a tank reactor with baffles with an internal volume of 40 L equipped with swept-back blades, and sodium hydroxide of BPA is supplied to it at a flow rate of 2.8 L/hr. As an aqueous solution, a 25 mass % sodium hydroxide aqueous solution was supplied at a flow rate of 0.07 L/hr, water was supplied at a flow rate of 17 L/hr, a 1 mass % triethylamine aqueous solution was supplied at a flow rate of 0.64 L/hr, and a 149.2 kg/hr flow rate was supplied A methylene chloride solution of 20% by mass of p-tert-butylphenol (PTBP) was supplied, and the reaction was performed at 29 to 32°C. The reaction solution was continuously withdrawn from the tank reactor and left to stand, whereby the water phase was separated and removed, and the dichloromethane 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) Manufacture of polycarbonate resin

Add 19 L of the above-mentioned oligomer solution and 11 L of dichloromethane to a tank reactor with an internal volume of 50 L equipped with baffle plates and paddle-type stirring blades, and dissolve the 3-pentadecyl group with a purity of 99.33% by mass obtained in Preparation Example 1. After 361 g of phenol (m-PDP) and 64 g of PTBP, 5.6 mL of triethylamine was added, and 1814 g of a 6.4 mass % sodium hydroxide aqueous solution was added thereto with stirring, and the reaction was carried out for 10 minutes. A sodium hydroxide aqueous solution of BPA (a solution obtained by dissolving 701 g of NaOH and 2.9 g of sodium dithionite in 10.8 L of water, and dissolving 1462 g of BPA in the obtained aqueous solution) was added, and polymerization reaction was performed for 50 minutes.

After adding 4 L of dichloromethane for dilution and stirring for 10 minutes, it separated into an organic phase containing polycarbonate and an aqueous phase containing excess bisphenol A and NaOH, and the organic phase was separated. The methylene chloride solution of the polycarbonate resin obtained is washed successively with 0.03mol/L sodium hydroxide aqueous solution and 0.2mol/L hydrochloric acid of 15% by volume relative to the solution, and then repeatedly washed with pure water to the water after washing. The electrical conductivity in the phase is 0.5 mS/m or less. The dichloromethane solution of the polycarbonate resin obtained by washing was concentrated and pulverized, and the obtained flake was dried under reduced pressure at 100° C. 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 380nm light transmittance of polycarbonate resin is 87.95%.

Manufacturing example 2

〔Manufacture 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 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 380nm light transmittance of polycarbonate resin is 87.90%.

Manufacturing example 3

〔Manufacture of polycarbonate resin (A-1)〕

Except that in the production of (2) polycarbonate resin in Production Example 1, 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, using the same method as in Production Example 1. method to obtain polycarbonate resin. 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 380nm light transmittance of polycarbonate resin is 86.92%.

Manufacturing example 4

〔Manufacture of polycarbonate resin (A-1)〕

Except that in the production of (2) polycarbonate resin in Production Example 1, 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, using the same method as in Production Example 1. method to obtain polycarbonate resin. 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 380nm light transmittance of polycarbonate resin is 87.60%.

Manufacturing Example 5

〔Manufacture 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 380nm light transmittance of polycarbonate resin is 87.86%.

Examples 1-14, Comparative Examples 1-4

〔Manufacture of polycarbonate resin composition〕

To 100 parts by mass of the polycarbonate resin (A) recorded in Table 1, mix 0.05 parts by mass of the phosphorus-based antioxidant (B) listed in Table 1, and then mix the fats listed in Table 1 at the ratio listed in Table 1 A cyclic epoxy compound (C) and a polyorganosiloxane (D) with a functional group were melt-kneaded and extruded using a 40mmφ single-screw extruder with a vent at a resin temperature of 280°C and a screw speed of 1000ppm. and granulated to obtain granules of the polycarbonate resin composition.

The performance evaluation methods of the molding materials and moldings used are shown below. The results are shown in Table 1.

(A-1) Ingredients

"PDP1100-5" Polycarbonate resin obtained in Production Example 1

Polycarbonate resin obtained in Production Example 2 of "PDP1300-5"

Polycarbonate resin obtained in Production Example 3 of "PDP1200-1"

Polycarbonate resin obtained in Production Example 4 of "PDP1200-3"

Polycarbonate resin obtained in Production Example 5 of "PDP1200-5"

(A-2) Ingredients

"Tarflon FN1200" (manufactured by Idemitsu Kosan Co., Ltd., bisphenol A polycarbonate resin, viscosity average molecular weight (Mv) = 11500)

"Tarflon FN1500" (manufactured by Idemitsu Kosan Co., Ltd., bisphenol A polycarbonate resin, viscosity average molecular weight (Mv) = 14500)

(B) Ingredients

"Adekastab PEP-36" (manufactured by ADEKA Co., Ltd., bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite)

"Doverphos S-9228PC" (made by Dover Chemical, bis(2,4-dicumylphenyl) pentaerythritol diphosphite)

(C) Ingredients

"Celloxide 2021P" (3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate, manufactured by Daicel Chemical Industry Co., Ltd.)

(D) Ingredients

"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 melt fluidity MVR (cm ³ /10 min) of the pellets obtained by the above method was measured at 300° C. under a load of 1.2 kg using Yasuda Seiki Co., Ltd., machine name MFR Meter No. E.

(2) YI value

Using the pellets obtained above, under the cylinder temperature setting of 320° C., a mold temperature of 80° C. and a cycle time of 50 seconds were used to form a flat plate-shaped molded body of 50 mm×90 mm×thickness 5 mm. The YI value of the obtained molded article was measured under conditions of a C light source and a 2-degree field of view using a spectrophotometer.

(3) YI value (350°C, 3 minutes) and YI value (350°C, 10 minutes)

The pellets obtained by the above method were subjected to a residence thermal stability test by injection molding as follows, and the YI values of the molded products having a residence time of 3 minutes and 10 minutes were measured.

<Injection Molding>

Injection molding machine: Toshiba Machine Co., Ltd. EC40N (trade name)

Formed product shape: 80mm×40mm×3.2mm

Forming machine barrel temperature: 350°C

Residence time in barrel: 3 minutes or 10 minutes

Mold temperature: 80°C

(4) Bending strength

Under the barrel temperature setting of 350° C., a mold temperature of 110° C. and a cycle time of 50 seconds were used to form a flat plate-shaped molded body of 50 mm×90 mm×thickness 0.5 mm. The obtained molded body was placed on a 50 mm wide jig set at 30 mm between fulcrums, and a test was performed at a test speed of 0.5 mm/m to measure the bending strength of the molded body.

[Table 1]

According to the comparison of the above-mentioned Examples 1-14 and Comparative Examples 1-4, it can be seen that the resin composition containing polycarbonate resin produced by using high-purity 3-pentadecylphenol as an end-capping agent belonging to the present invention is different from the conventional resin composition containing Compared with the resin composition of polycarbonate resin, it has excellent fluidity, a low YI value, excellent color tone and transparency, and excellent molding stability at high temperature.

Industrial availability

The polycarbonate resin composition of the present invention can obtain a molded article with excellent fluidity, excellent light transmittance and brightness, excellent molding stability at high temperature, and excellent light transmittance, even if the molded article is placed in a high-temperature and high-humidity environment for a long time , and no discoloration or deterioration will occur. Therefore, the polycarbonate resin composition of the present invention can be used particularly as an optical molded article, especially as a light guide plate, and also as a light guide plate for a thin-walled large-screen liquid crystal display device.

Claims (15)

1. A polycarbonate resin composition comprising 10 to 100% by mass of polycarbonate resin (A-1) and 90% of polycarbonate resin (A-2) other than (A-1) ～0 mass % polycarbonate resin (A) 100 mass parts, contain phosphorus antioxidant (B) 0.005～0.5 mass part, described polycarbonate resin (A-1) uses as raw material and contains following general formula ( I) The resorcinol derivative represented by 1% by mass or less and/or the phenol derivative represented by the following general formula (II) is 2.5% by mass or less, the total content of the resorcinol derivative and the phenol derivative is The polycarbonate resin (A-1) is molded at a temperature of 350° C. to a thickness of 3 mm. The light transmittance at 380nm is above 85.0%; In the formula, R ¹ and R ² are a hydrogen atom, or an aliphatic hydrocarbon group with 1 to 20 carbon atoms; R ³ is a hydrogen atom, or a saturated or unsaturated aliphatic hydrocarbon group with 1 to 20 carbon atoms; R ¹ , R ^2. R ³ may be the same or different; however, in the above general formula (II), 3-pentadecylphenol represented by R ¹ =H, R ³ =C ₁₅ H ₃₁ is excluded. 2. polycarbonate resin composition according to claim 1, wherein, Furthermore, 0.001-0.5 mass parts of aliphatic cyclic epoxy compounds (C) are contained with respect to 100 mass parts of said (A) components. 3. polycarbonate resin composition according to claim 1 or 2, wherein, The purity of the 3-pentadecylphenol is 99.0% by mass or more. 4. The polycarbonate resin composition according to any one of claims 1 to 3, wherein, The 3-pentadecylphenol is obtained by crystallization after distillation. 5. The polycarbonate resin composition according to any one of claims 1 to 4, wherein, Content of the 3-pentadecylphenoxy group in the said (A) component is 0.1-10 mass %. 6. The polycarbonate resin composition according to any one of claims 1 to 5, wherein, The said (B) component has a pentaerythritol structure. 7. The polycarbonate resin composition according to any one of claims 1 to 6, wherein, The component (B) is bis(2,4-dicumylphenyl)pentaerythritol diphosphite represented by the following general formula, 8. The polycarbonate resin composition according to any one of claims 2 to 7, wherein, The (C) component is selected from 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate, 2,2-bis(hydroxymethyl)-1- At least one of 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of butanol and mixtures thereof. 9. The polycarbonate resin composition according to any one of claims 1 to 8, It further contains 0.02-0.15 mass parts of polyorganosiloxane (D) which has a functional group with respect to 100 mass parts of said (A) components. 10. polycarbonate resin composition according to claim 9, wherein, The functional group is at least one selected from 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. 11. polycarbonate resin composition according to claim 9 or 10, wherein, The difference between the refractive index of the functional group-containing polyorganosiloxane (D) and the polycarbonate resin (A) is 0.13 or less. 12. The polycarbonate resin composition according to any one of claims 1 to 11, wherein, The polycarbonate resin (A) has a viscosity average molecular weight of 8,000-19,000. 13. A molded article formed by molding the polycarbonate resin composition according to any one of claims 1 to 12. 14. The shaped body according to claim 13, wherein, The molded body is a light guide member. 15. The shaped body according to claim 14, wherein, The light guide member is a light guide plate.