JP6610104B2 - Polycarbonate resin, method for producing polycarbonate resin, and method for producing polycarbonate resin molded body - Google Patents

Description

  The present invention relates to a polycarbonate resin. Specifically, the present invention relates to a polycarbonate resin excellent in balance of transparency, impact strength, and moldability, and a molded body formed by molding the polycarbonate resin.

Polycarbonate resin is excellent in heat resistance, mechanical strength, electrical characteristics, and dimensional stability. For example, they are used in a wide range of fields such as automobile members, electrical / electronic / OA equipment, information / communication equipment, household electrical appliances, housing materials, and other parts manufacturing materials in industrial fields.
However, since the aromatic polycarbonate resin is an amorphous resin having high heat resistance, it has the disadvantages of high molding processing temperature and low melt fluidity. In recent years, parts are becoming larger and integrated in the automobile field, and parts are being made lighter, thinner and shorter in the electrical and electronic equipment field. In such a flow, improvement of moldability of the polycarbonate resin has been a problem.

  As a technique for improving the moldability of the polycarbonate resin, it is the easiest and simplest technique to lower the molecular weight. However, in this case, it is inevitable that the mechanical properties of the polycarbonate resin are lowered. Among them, particularly the impact resistance is significantly reduced. Therefore, from the viewpoint of the impact resistance of the polycarbonate resin, the range in which this method can be applied is considerably limited.

In addition, a method of alloying polycarbonate resin by mixing styrene resin or acrylic resin is also widely known, but this method also inevitably reduces impact resistance, and also deteriorates the transparency of polycarbonate resin. To do.
On the other hand, attempts have been made to improve the fluidity while maintaining the transparency by making the end group of the polycarbonate resin specific (for example, Patent Documents 1 and 2).
However, even if any of these methods is used, the impact resistance of the polycarbonate resin is lowered, so that it cannot withstand actual use.

JP 7-26007 A JP-A-1-275629

  In view of the above problems, the present invention provides a polycarbonate resin excellent in balance of transparency, impact strength, and moldability, a method for producing the polycarbonate resin, and a method for producing a polycarbonate resin molded body obtained by molding the polycarbonate resin. With the goal.

As a result of intensive studies, the present inventors have found that a polycarbonate resin containing a specific carbonate structural unit is excellent in balance of transparency, impact resistance, and moldability, and has completed the present invention.
That is, the gist of the present invention resides in the following [1] to [7].
[1] At least a carbonate structural unit (A) represented by the following formula (1) and the following formula (2)
A polycarbonate resin comprising a carbonate structural unit (B) represented by

[In formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms. ]

[2] The polycarbonate resin according to [1], wherein the carbonate structural unit (A) is represented by the following formula (3).

[3] JIS (1999 version) K7210 According to Annex C, the flow value (Q value) measured under the conditions of 280 ° C. and 160 kgf using a Koka flow tester is 10 (unit: 10 ^−2). cm ³ / sec) or more, [1] or [2] polycarbonate resin.
[4] The polycarbonate resin according to any one of [1] to [3], wherein the ratio of the carbonate structural unit (A) to the total carbonate structural unit in the polycarbonate resin is 1 to 55 mol%.
[5] The polycarbonate according to any one of [1] to [4], wherein a haze value measured in accordance with JIS K7136: 2000 is 1 or less when the molded product is 3 mm thick. resin.
[6] A method for producing a polycarbonate resin, wherein the polycarbonate resin according to any one of [1] to [5] is produced by a melt transesterification method.
[7] A method for producing a polycarbonate resin molded body, wherein the polycarbonate resin according to any one of [1] to [6] is molded by injection molding.

  According to the polycarbonate resin of the present invention, a polycarbonate resin having an excellent balance of transparency, impact strength, and moldability can be provided. Such a polycarbonate resin is extremely useful in the industry because a thin and large transparent molded article having excellent mechanical strength such as impact resistance can be obtained with high productivity.

Hereinafter, although an embodiment, an example thing, etc. are shown and explained in detail about the present invention, the present invention is limited to an embodiment, an example, etc. shown below and is not interpreted.
In the present specification, unless otherwise specified, “to” is used in a sense that includes numerical values described before and after it as a lower limit value and an upper limit value. Further, “part” means a part by mass based on the mass standard unless otherwise specified.

<1. Polycarbonate resin>
The polycarbonate resin of the present invention includes at least a carbonate structural unit (A) represented by the following formula (1) and a carbonate structural unit (B) represented by the following formula (2). By including the carbonate structural units (A) and (B) in this manner, the impact resistance of the polycarbonate resin of the present invention is increased, and even when the fluidity is adjusted to be high in order to improve the moldability, the impact resistance is also good. Can be maintained.

In formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Among them, an ethyl group and an n-butyl group are preferable, and n-butyl is preferable. The group is particularly preferred. Specifically, the carbonate structural unit represented by the following formula (3) is preferably used as the carbonate structural unit (A) in which R ¹ in the formula (1) is an n-butyl group.

The polycarbonate resin of the present invention includes a carbonate structural unit (A) and a carbonate structural unit (B), even a copolymer composed only of the carbonate structural unit (A) and the carbonate structural unit (B). Although it may be a copolymer (copolymer) containing at least one carbonate structural unit derived from another dihydroxy compound, which is different from the structural unit, preferably, the carbonate structural unit (A) and the carbonate structural unit (B). It is a copolymer composed only of

  Other dihydroxy compounds containing a carbonate structural unit (A) and a carbonate structural unit (B) and derived from a carbonate structural unit different from these two types of carbonate structural units can be used in any combination and in any ratio. May be included. Moreover, as a copolymerization form of a copolymer, various copolymerization forms, such as a random copolymer and a block copolymer, can be selected.

  The other dihydroxy compound is not particularly limited, and may be an aromatic dihydroxy compound having an aromatic ring in the molecular skeleton or an aliphatic dihydroxy compound having no aromatic ring. In addition, a dihydroxy compound into which a hetero atom or hetero bond such as N (nitrogen), S (sulfur), P (phosphorus), or Si (silicon) is introduced may be used for imparting various properties.

As other dihydroxy compounds different from those described above, aromatic dihydroxy compounds are preferably used from the viewpoints of heat resistance, thermal stability and strength. Specific examples of such aromatic dihydroxy compounds include the following. Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene; 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4 ′ -Dihydroxybiphenyls such as dihydroxybiphenyl; 2,2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene , 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like; 2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiph Dihydroxy diaryl ethers such as phenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) benzene, 1,3-bis (4-hydroxyphenoxy) benzene; 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methoxy-4-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) ) Propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-cyclohexyl) -4-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-cyclohexyl) -4-hydroxyphenyl) propane, α, α'-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) cyclohexylmethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) (4-propenylphenyl) methane, bis (4-hydroxyphenyl) Diphenylmethane, bis (4-hydroxyphenyl) naphthylmethane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) -1-naphthy Bis (hydroxyaryl) alkanes such as ethane, 1-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) butane; 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis ( 4-hydroxyphenyl) cyclohexane, 4-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1-bis (4-hydroxyphenyl) -3,4 -Dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis ( 4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohex 1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane, 1,1-bis (4 -Hydroxyphenyl) -3-tert-butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane, etc. Hydroxyaryl) cycloalkanes; cardiostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 4,4′-dihydroxy Diphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfur Dihydroxy diaryl sulfides such as 4,4′-dihydroxydiphenyl sulfoxide, dihydroxy diaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; 4,4′-dihydroxydiphenyl sulfone, 4 , 4′-dihydroxy-3,3′-dimethyldiphenylsulfone, and the like; and the like.

In addition, 1 type may be used for a dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.
In the polycarbonate resin of the present invention, the molar fraction of the carbonate structural unit (A) relative to the total carbonate structural unit is not particularly limited as long as the characteristics of the polycarbonate resin of the present invention are not impaired, but preferably 0.5 to 80 mol. %, More preferably 1 to 55 mol%, still more preferably 2 to 30 mol%, and particularly preferably 3 to 20 mol%.

As the molar fraction of the carbonate structural unit (A) decreases, the moldability and impact resistance of the polycarbonate resin of the present invention may decrease. On the other hand, as the molar fraction of the carbonate structural unit (A) increases. The heat resistance of the polycarbonate resin of the present invention may be extremely lowered.
The polycarbonate resin of the present invention includes a dihydroxy compound derived from the above carbonate structural unit (A), a dihydroxy compound derived from the above carbonate structural unit (B) (so-called bisphenol A), and other dihydroxy compounds optionally selected. It can be obtained by polycondensing a dihydroxy compound containing a compound with a carbonate-forming compound.

  The dihydroxy compound derived from the carbonate structural unit (A) is a dihydroxy compound represented by the following formula (4).

In formula (4), R ² represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.
Among these, as the dihydroxy compound derived from the carbonate structural unit (A), dihydroxy compounds of the following formulas (5) and (6) are preferable, and dihydroxy compounds of the following formula (6) are more preferable.

  Such a dihydroxy compound can be synthesized and produced from an aldehyde compound represented by the following formula (7) and phenol, and the synthesis reaction and production method can be obtained by known methods.

In formula (7), R ³ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Examples of such aldehyde compounds include 2-ethylbutanal and 2-ethylhexanal.
As examples of the carbonate-forming compound, carbonyl halide, carbonate ester and the like are used. In addition, a carbonate forming compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.
Specific examples of the carbonate ester include compounds represented by the following formula (8): aryl carbonates, dialkyl carbonates, biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, cyclic carbonates And carbonate bodies of dihydroxy compounds such as

In Formula (8), R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms, an aryl group, or an arylalkyl group. Hereinafter, when R ⁴ and R ⁵ are an alkyl group or an arylalkyl group, they may be referred to as dialkyl carbonate, and when they are an aryl group, they may be referred to as diaryl carbonate. Among these, from the viewpoint of reactivity with the dihydroxy compound, both R ⁴ and R ⁵ are preferably aryl groups, and more preferably diaryl carbonates represented by the following formula (9).

In formula (9), R ⁶ and R ⁷ each independently represent a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or 4 to 20 carbon atoms. And an aryl group having 6 to 20 carbon atoms, p and q each independently represent an integer of 0 to 5.
Specific examples of such carbonate esters include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, diphenyl carbonate (hereinafter sometimes referred to as “DPC”), and bis (4-methyl). Phenyl) carbonate, bis (4-chlorophenyl) carbonate, bis (4-fluorophenyl) carbonate, bis (2-chlorophenyl) carbonate, bis (2,4-difluorophenyl) carbonate, bis (4-nitrophenyl) carbonate, bis (Substituted) diaryl carbonates such as (2-nitrophenyl) carbonate, bis (methylsalicylphenyl) carbonate, and ditolyl carbonate are exemplified, and among them, diphenyl carbonate is preferable. In addition, these carbonate ester can be used individually or in mixture of 2 or more types.

  In addition, the carbonate ester may be preferably substituted with dicarboxylic acid or dicarboxylic acid ester in an amount of 50 mol% or less, more preferably 30 mol% or less. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

<Production method of polycarbonate resin>
The method for producing the polycarbonate resin of the present invention can be produced by a conventionally known polymerization method. In the present invention, the polymerization method for producing the polycarbonate resin is not particularly limited. Examples of the polymerization method include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, a particularly preferable one of these methods will be specifically described.

Interfacial Polymerization Method First, the case where the polycarbonate resin of the present invention is produced by the interfacial polymerization method will be described. In the interfacial polymerization method, in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, the pH is usually kept at 9 or higher, and the raw material dihydroxy compound and a carbonate-forming compound (preferably phosgene) are reacted, A polycarbonate resin is obtained by performing interfacial polymerization in the presence of a polymerization catalyst. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

The raw material dihydroxy compound and carbonate-forming compound are as described above. Of the carbonate-forming compounds, phosgene is preferably used, and the method using phosgene is particularly called a phosgene method.
The organic solvent inert to the reaction is not particularly limited, but examples thereof include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic carbonization such as benzene, toluene and xylene. Hydrogen; and the like. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include, but are not limited to, alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate. Sodium hydroxide and potassium hydroxide are preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the raw dihydroxy compound to the alkali compound is usually 1: 1. In order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. It is preferably 9 or more, particularly 1: 2.0 or more, and usually 1: 3.2 or less, particularly 1: 2.5 or less.

  The polymerization catalyst is not particularly limited, and examples thereof include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine; N, N′-dimethylcyclohexylamine, N, N′-diethylcyclohexyl Alicyclic tertiary amines such as amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; tertiary amines such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride Quaternary ammonium salts, etc .; pyridine; guanine; guanidine salts; In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

The molecular weight regulator is not particularly limited, and examples thereof include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. preferable. Specific examples of such aromatic phenols include phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot-butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn- Hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on- Nylphenol, m-nonylphenol, pn-nonylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol; 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; p-cresol, bromophenol, tri Bromophenol, monoalkylphenol having a linear or branched alkyl group having an average carbon number of 12 to 35 at the ortho, meta or para position; 9- (4-hydroxyphenyl) -9- (4-methoxyphenyl) Fluorene; 9- (4-hydroxy-3-methylphenyl) -9- (4-methoxy-3) Methylphenyl) fluorene; 4- (1-
Adamantyl) phenol and the like. Of these, pt-butylphenol, p-phenylphenol and p-cumylphenol are preferably used. In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

The amount of the molecular weight regulator used is not particularly limited, but is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 with respect to 100 mol of the raw dihydroxy compound. It is below the mole. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of polycarbonate resin can be improved.
In the reaction, the order of mixing the reaction substrate (reaction raw material), reaction medium (organic solvent), catalyst, additive, etc. is arbitrary as long as the desired polycarbonate resin is obtained, and the appropriate order can be arbitrarily set. That's fine. For example, when phosgene is used as the carbonate-forming compound, the molecular weight regulator is mixed at any time as long as it is between the reaction (phosgenation) of the raw dihydroxy compound and phosgene and the start of the polymerization reaction. it can.
In addition, although reaction temperature is not specifically limited, Usually, it is 0-40 degreeC, Reaction time is not specifically limited, Usually, it is several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

Melt transesterification process will be described for the case of producing the polycarbonate resin of the present invention in the melt transesterification process. In the melt transesterification method, for example, an ester exchange reaction between a carbonate ester and a raw material dihydroxy compound is performed.
The raw material dihydroxy compound and carbonate ester are as described above.
The ratio of the raw material dihydroxy compound and the carbonate ester is arbitrary as long as the desired polycarbonate resin is obtained, but it is preferable to use an equimolar amount or more of the carbonate ester with respect to 1 mol of the dihydroxy compound. More preferably, it is used. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups of the obtained polycarbonate resin can be adjusted to a suitable range.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. A transesterification catalyst is not specifically limited, A conventionally well-known thing can be used. For example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

In the melt transesterification method, the reaction temperature is not particularly limited, but is usually 100 to 320 ° C. Moreover, the pressure at the time of reaction is not particularly limited, but is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product.
The reaction can be carried out either batchwise or continuously. In the case of a batch system, the order of mixing the reaction substrate, reaction medium, catalyst, additive, etc. is arbitrary as long as the desired polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. However, considering the stability of the polycarbonate resin, the melt polycondensation reaction is preferably carried out continuously.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof, phosphorus-containing compounds and derivatives thereof, and the like. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst deactivator used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more with respect to the alkali metal or alkaline earth metal contained in the transesterification catalyst, Usually, it is 10 equivalents or less, preferably 8 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to polycarbonate resin, and is 100 ppm or less normally, Preferably it is 50 ppm or less.

<Physical properties of polycarbonate resin>
Molecular Weight of Polycarbonate Resin The molecular weight of the polycarbonate resin of the present invention is not particularly limited as long as it does not impair the characteristics of the polycarbonate resin of the present invention, but it is a viscosity average molecular weight (Mv) converted from the solution viscosity and is usually 8000 to 50000. , Preferably it is 10000-30000, More preferably, it is 11000-28000. By making the viscosity average molecular weight more than the lower limit of the above range, the mechanical strength of the polycarbonate resin of the present invention and the polycarbonate resin composition of the present invention can be further improved, and used for applications requiring high mechanical strength. It may be preferable in some cases. On the other hand, when the viscosity average molecular weight is not more than the upper limit of the above range, the flowability of the polycarbonate resin and the polycarbonate resin composition of the present invention is improved, and the molding processability is improved and the molding process is facilitated. In addition, when controlling the viscosity average molecular weight of the polycarbonate resin of the present invention within the above range, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, the viscosity average molecular weight is The viscosity average molecular weight (Mv) of the polycarbonate resin of the present invention may be controlled by mixing using a polycarbonate resin that is outside the above preferred range.

The viscosity average molecular weight (Mv) of the polycarbonate resin of the present invention is determined by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer, It means a value calculated from Schnell's viscosity equation, that is, η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity η _sp at each solution concentration C (g / dl).

Glass transition temperature (Tg) of polycarbonate resin
The glass transition temperature of the polycarbonate resin of the present invention is not particularly limited as long as it does not impair the characteristics of the polycarbonate resin of the present invention, but is usually 90 ° C or higher, preferably 100 ° C or higher, more preferably 110 ° C or higher, More preferably, it is 120 degreeC or more, Most preferably, it is 130 degreeC or more, Usually, 150 degreeC or less, Preferably it is 148 degreeC or less, More preferably, it is 145 degreeC or less, More preferably, it is 140 degreeC or less. When Tg is less than the lower limit of the above range, the heat resistance of the polycarbonate resin and the polycarbonate resin composition of the present invention is remarkably inferior. On the other hand, when the upper limit of the above range is exceeded, the moldability of the polycarbonate resin and the polycarbonate resin composition of the present invention is remarkably lowered, which is also not preferable.

The amount of terminal hydroxyl groups of the polycarbonate resin The amount of terminal hydroxyl groups of the polycarbonate resin of the present invention is not particularly limited as long as it does not impair the characteristics of the polycarbonate resin of the present invention, but is usually 10 to 2000 ppm. If the amount of terminal hydroxyl groups is not less than the lower limit of the above range, the polycarbonate resin of the present invention, and the hue of the polycarbonate resin composition, productivity can be further improved, and if not more than the upper limit of the above range, The heat stability and wet heat stability of the polycarbonate resin and the polycarbonate resin composition of the present invention can be further improved. From such a viewpoint, the amount of terminal hydroxyl groups of the polycarbonate resin of the present invention is more preferably 50 to 1500 ppm, and particularly preferably 70 to 1000 ppm.

  The amount of terminal hydroxyl groups of the polycarbonate resin of the present invention can be adjusted to the above range by any known method. For example, when the polycarbonate resin of the present invention is produced by polycondensation by transesterification, the amount of terminal hydroxyl groups is adjusted by adjusting the mixing ratio of carbonate ester and dihydroxy compound; Can be adjusted to the range. In addition, the molecular weight of the obtained polycarbonate resin can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonate ester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.
Moreover, when manufacturing the polycarbonate resin of this invention by an interfacial polymerization method, the amount of terminal hydroxyl groups can be adjusted arbitrarily by adjusting the compounding quantity of a molecular weight modifier (terminal terminator).
In addition, the unit of a terminal hydroxyl group density | concentration represents the mass of the terminal hydroxyl group with respect to the mass of polycarbonate resin in ppm. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

Q value of polycarbonate resin According to JIS (1999 version) K7210 Annex C of the polycarbonate resin of the present invention, the flow value (Q value) measured under the conditions of 280 ° C. and 160 kgf using an elevated flow tester is , Preferably 4 (unit: 10 ⁻² cm ³ / sec) or more, more preferably 10 or more, still more preferably 11 or more, and particularly preferably 12 or more. The Q value is an index of melt viscosity, and a higher value represents lower melt viscosity and better moldability. In general bisphenol A type polycarbonate resins, as the Q value increases, that is, as the viscosity decreases, the molecular weight decreases and the mechanical strength including impact resistance significantly decreases. On the other hand, the polycarbonate resin of the present invention can maintain high impact strength when compared with a melt viscosity equivalent to that of a general bisphenol A type polycarbonate resin.

Haze value of polycarbonate resin The polycarbonate resin of the present invention is characterized by excellent transparency. Transparency can be represented by a haze value (unit:%) measured in accordance with JIS K7136: 2000 when formed into a 3 mm thick molded article, and is usually 5 or less, preferably 3 or less, more preferably 1 Hereinafter, more preferably, it is 0.8 or less.

Other Components The polycarbonate resin of the present invention may be a resin composition containing other resins and various additives as long as the effects of the present invention and desired physical properties are not significantly impaired. When the example of other resin is given, Preferably, polycarbonate resin other than the polycarbonate resin of this invention, resin other than polycarbonate resin, etc. are mentioned. Various additives include heat stabilizers, antioxidants, mold release agents, lubricants, ultraviolet absorbers, fluorescent brighteners, brightness improvers, flame retardants, dyes and pigments, antistatic agents, antifogging agents, An antiblocking agent, a dispersing agent, an antibacterial agent, etc. are mentioned. In addition, 1 type may contain other resin and various additives, and 2 or more types may contain them by arbitrary combinations and ratios.

<Production method of polycarbonate resin composition>
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely.
Specific examples include polycarbonate resin and other ingredients that are blended as necessary, for example, using a mixer such as a tumbler or Henschel mixer, and then mixed with a Banbury mixer, roll, Brabender, single-screw kneading extrusion, etc. And a melt kneading method using a mixer such as a machine, a twin-screw kneading extruder, or a kneader.

In addition, for example, without mixing each component in advance, or only a part of the components is mixed in advance, and fed to an extruder using a feeder and melt-kneaded to produce the polycarbonate resin composition of the present invention. You can also.
Further, when the polycarbonate resin of the present invention is produced, an additive may be directly added to the molten resin after the polymerization and kneaded. When adding in this way, it is preferable to introduce the molten resin directly into the extruder after the polymerization, mix the additive, melt knead and pelletize.

Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. The polycarbonate resin composition of the present invention can also be produced.
In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.

<Molded body>
The molded body of the present invention is obtained by molding the polycarbonate resin or polycarbonate resin composition of the present invention, and among them, a molded body obtained by injection molding is preferable.
Moreover, there is no restriction | limiting in the shape, pattern, color, dimension, etc. of the molded object of this invention, According to the use of the molded object, it can select suitably, for example, plate shape, plate shape, rod shape, sheet shape, Various shapes such as film, cylindrical, annular, circular, elliptical, polygonal, irregular, hollow, frame, box, panel, etc., and special shapes It is done. Further, for example, the surface may be uneven or may have a three-dimensional curved surface.

  The molding method can be arbitrarily selected from the molding methods generally used for polycarbonate resins. For example, injection molding, ultra-high speed injection molding, injection compression molding, two-color molding, gas Hollow molding method such as assist, molding method using heat insulating mold, molding method using rapid heating mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion Examples include a molding method, a sheet molding method, a thermoforming method, a rotational molding method, a lamination molding method, a press molding method, a blow molding method, etc. The polycarbonate resin of the present invention is a polycarbonate resin molding obtained by molding by injection molding. It is preferable to manufacture. A molding method using a hot runner method can also be used.

Examples of the molded body include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is particularly suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment.
Among them, it can be preferably used for display members mainly using optical parts, particularly liquid crystal displays (LCDs) by making use of excellent fluidity (moldability), transparency and strength. Among such display members, it can be suitably used for a light guide plate installed inside a backlight unit that guides light mounted on a display device.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
[Example 1]
A 2,2'-bis (4-hydroxyphenyl) propane (Mitsubishi Chemical Corporation) as a raw material dihydroxy compound was added to a 150 ml glass reactor with a reactor stirrer, reactor heating device, and reactor pressure regulator. 101.9 g), and 14.8 g of 1,1-bis (4-hydroxyphenyl) -2-ethylhexane (Tokyo Chemical Industry Co., Ltd.) represented by the above formula (6), and diphenyl carbonate (Mitsubishi) (Chemical Co., Ltd.) 112.1 g was added, and then cesium carbonate was added as a catalyst at a rate of 1 μmol / mol with respect to a total of 1 mol of dihydroxy compounds.

  Next, the operation of depressurizing the inside of the glass reactor to about 100 Pa (0.75 Torr) and then restoring the pressure to the atmospheric pressure with nitrogen was repeated three times to replace the inside of the reactor with nitrogen. After the nitrogen replacement, the reactor external temperature was set to 220 ° C., the reactor internal temperature was gradually raised, and the mixture was dissolved. Then, the stirrer was rotated at 100 rpm. Then, while distilling off phenol by-produced by the oligomerization reaction of the dihydroxy compound and diphenyl carbonate performed in the reactor, the pressure in the reactor is increased from 101.3 kPa (760 Torr) to 13 in absolute pressure over 40 minutes. The pressure was reduced to 3 kPa (100 Torr).

  Subsequently, the transesterification reaction was carried out for 80 minutes while maintaining the pressure in the reactor at 13.3 kPa and further distilling off the phenol. Thereafter, the temperature outside the reactor is raised to 250 ° C., and the pressure inside the reactor is reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) over 40 minutes, and the distilled phenol is removed from the system. Removed. Thereafter, the external temperature of the reactor was further increased to 270 ° C., and the absolute pressure in the reactor was reduced to 30 Pa (about 0.2 Torr) to carry out a polycondensation reaction. The polycondensation reaction was terminated when the agitator of the reactor reached a predetermined stirring power. Next, the inside of the reactor was restored to an absolute pressure of 101.3 kPa with nitrogen and then increased to 0.2 MPa with a gauge pressure, and the polycarbonate resin was taken out of the reactor.

[Create specimen]
After drying the polycarbonate resin obtained above at 100 ° C. for 5 hours, using a J5S type injection molding machine manufactured by Nippon Steel Co., Ltd. under the conditions of a cylinder set temperature of 260 ° C., a mold temperature of 40 ° C., and a screw rotation speed of 100 rpm. Then, a flat plate-shaped test piece having a thickness of 48 mm × 15 mm × 1 mm and an Izod impact test piece having a thickness of 3.2 mm conforming to ASTM D-256 were injection molded.
The terminal hydroxyl group concentration and the viscosity average molecular weight were measured by the methods described above.

[Glass transition temperature evaluation]
Using a differential operation calorimeter (DSC 6220, manufactured by SII), about 10 mg of a polycarbonate resin sample is heated at a rate of temperature increase of 20 ° C./min to measure the amount of heat. In accordance with JIS-K7121, a baseline on the low temperature side is measured. The extrapolated glass transition start temperature, which is the temperature at the intersection of the straight line extended to the high temperature side and the tangent drawn at the point where the slope of the step-like change portion of the glass transition is maximized, was determined. The extrapolated glass transition temperature was defined as the glass transition temperature (Tg). Higher Tg represents better heat resistance and is preferable.

[Fluidity evaluation]
The flow rate (Q value) of the pellets was evaluated by the method described in 1999 edition JIS K7210 Appendix C as an evaluation of fluidity. Measurement was conducted using a CFT-500A flow tester manufactured by Shimadzu Corporation, using a die having a hole diameter of 1.0 mmφ and a length of 10 mm, under conditions of a test temperature of 280 ° C., a test force of 160 kg / cm 2 and a preheating time of 420 sec. The amount of molten resin (unit: 10 ⁻² cm ³ / sec) was measured.
The Q value is an index of melt viscosity, and an equivalent value indicates an equivalent moldability.

[Impact resistance evaluation]
Using the Izod impact test piece obtained by the above-mentioned method, the Izod impact resistance with notch of R0.25 (unit: J / m) was evaluated according to the ASTM D-256 standard.
[Transparency evaluation]
The haze (unit:%) was evaluated based on the JIS K 7136: 2000 standard using the flat test piece obtained by the above method. Haze is an index of transparency, and a smaller value is preferable because it indicates higher transparency. In general, a highly transparent material is required to be 1% or less under the above conditions.

[Example 2]
As raw dihydroxy compounds, 50.6 g of 2,2′-bis (4-hydroxyphenyl) propane and 66.1 g of 1,1-bis (4-hydroxyphenyl) -2-ethylhexane were further added. Polymerization and evaluation were performed under the same conditions as in Example 1 except that 2 g was added and then cesium carbonate was added as a catalyst at a rate of 5 μmol / mol with respect to 1 mol of the total of dihydroxy compounds.

[Example 3]
As raw material dihydroxy compounds, 41.1 g of 2,2′-bis (4-hydroxyphenyl) propane and 80.6 g of 1,1-bis (4-hydroxyphenyl) -2-ethylhexane were further added. 7 g was added, and then polymerization / evaluation was performed under the same conditions as in Example 1 except that cesium carbonate was added as a catalyst at a rate of 5 μmol / mol with respect to 1 mol of the total of dihydroxy compounds.

[Comparative Example 1]
As the raw dihydroxy compound, 116.7 g of 2,2′-bis (4-hydroxyphenyl) propane and 118.8 g of diphenyl carbonate were added. Next, as a catalyst, cesium carbonate was used with respect to a total of 1 mol of the dihydroxy compound. Polymerization and evaluation were performed under the same conditions as in Example 1 except that the addition was performed at a rate of 0.5 μmol / mol.
The evaluation results are shown in Table 1.

From Table 1, when comparing Examples 1 to 3 containing carbonate structural unit (A) and Comparative Example 1 not containing carbonate structural unit (A), the equivalent melt viscosity (Q value is 13 to 14 10 ^-2 cm). ³ / sec), the Izod impact strength is higher in Examples 1 to 3 than in Comparative Example 1. In Examples 1 to 3 and Comparative Example 1, the transparency index (haze) is equivalent to 0.5 to 0.6%. According to a known technique, impact resistance can be increased by blending a rubber component or the like with the polycarbonate resin of Comparative Example 1, but in that case, it is obvious that transparency is deteriorated.

  In other words, the polycarbonate resin of the present invention has a high impact strength and does not sacrifice transparency even when adjusted with the same melt viscosity, so that the balance of transparency, impact strength, and moldability is achieved. Excellent polycarbonate resin.

Claims (6)

A polycarbonate resin comprising at least a carbonate structural unit (A) represented by the following formula (1) and a carbonate structural unit (B) represented by the following formula (2).

[In formula (1), ^{R 1} represents an alkyl group having 1 to 4 carbon atoms. ]

The polycarbonate resin according to claim 1, wherein the carbonate structural unit (A) is represented by the following formula (3).

According to JIS (1999 version) K7210 Annex C, a flow value (Q value) measured under the conditions of 280 ° C. and 160 kgf using a Koka type flow tester is 10 (unit: 10)
^-2 cm ^{< 3} > / sec) or more, The polycarbonate resin according to claim 1 or 2. The ratio of the said carbonate structural unit (A) with respect to all the carbonate structural units in the said polycarbonate resin is 1-55 mol%, The polycarbonate resin in any one of Claims 1-3. The manufacturing method of the polycarbonate resin which manufactures the polycarbonate resin of any one of Claims 1-4 by the melt transesterification method. The polycarbonate resin according to any one of claims 1 to 4 is molded by injection molding.
A method for producing a polycarbonate resin molded body.