JP6013525B2 - Polycarbonate resin composition and polycarbonate resin molded body - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a polycarbonate resin molded body.

Polycarbonate resins are also used in applications such as OA equipment and home appliances. In this field, there is a strong demand for flame retardant synthetic resin materials, and many flame retardants are being studied. For example, in Patent Document 1, in a polycarbonate resin composition in which 0.01 to 30 parts by weight of a flame retardant is blended with 100 parts by weight of a polycarbonate obtained by a melting method, measurement was performed at a temperature of 250 ° C. and an angular velocity of 10 rad / s. A polycarbonate resin composition is described in which the loss angle δ and the complex viscosity η ^* (Pa · s) of the polycarbonate satisfy the relational expression 2500 ≦ tan δ / η ^{* −0.87} ≦ 6000.

Japanese Patent Laid-Open No. 2003-090661

By the way, in a certain use of a polycarbonate resin, better flame retardancy is required than a normal polycarbonate resin.
The objective of this invention is improving the flame retardance of a polycarbonate resin composition.

According to this invention, the polycarbonate resin composition and polycarbonate resin molding which concern on following [1]-[8] are provided.
[1] A polycarbonate resin composition comprising a polycarbonate resin having a structural unit represented by the following formula (1) in the molecule and a flame retardant.

(In Formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group. R ³ and R ⁴ are Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, and X represents a single bond, a substituted or unsubstituted alkylene group, substituted or unsubstituted, Represents an unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom.)

[2] The polycarbonate resin composition according to [1], including 0.05 to 1 part by weight of the flame retardant with respect to 100 parts by weight of the polycarbonate resin.
[3] The flame retardant is at least one selected from the group consisting of metal sulfonate flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants. The polycarbonate resin composition according to [1] or [2].

[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the polycarbonate resin satisfies the following conditions (a) to (e):
(A) The intrinsic viscosity [η] (dl / g) at 20 ° C. in a methylene chloride solvent is in the range of 0.40 to 2.0.
(B) The branch parameter G = [η] / [η] _lin is in the range of 0.1 to 0.9. However, [η] _lin is an intrinsic viscosity at 20 ° C. in a methylene chloride solvent of a linear polycarbonate having the same weight average molecular weight measured by a light scattering method or a GPC method using a general-purpose calibration curve.
(C) The logarithmic value lnη ^* ₁₀ of the melt viscosity (Pa · s) at 300 ° C. and a shear rate of ₁₀ sec ⁻¹ measured with a capillary rheometer is the intrinsic viscosity [η] (dl / g at 20 ° C. in a methylene chloride solvent. ) Divided by lnη ^* ₁₀ / [η] is in the range of 10.0 to 15.0.
(D) The logarithmic value lnη ^* ₁₀₀₀ of the melt viscosity (Pa · s) at 300 ° C. and a shear rate of 1000 sec ⁻¹ measured with a capillary rheometer is the intrinsic viscosity [η] (dl / g at 20 ° C. in a methylene chloride solvent. The numerical value lnη ^* ₁₀₀₀ / [η] divided by) is in the range of 8.0 to 11.0.
(E) The pencil hardness according to JIS K5400 is HB or higher.

[5] R ¹ and R ² in Formula (1) of the polycarbonate resin are a methyl group bonded to the carbon at the 3-position of the phenyl group, and R ³ and R ⁴ are hydrogen bonded to the carbon at the 5-position of the phenyl group The polycarbonate resin composition according to any one of [1] to [4], wherein the atom and X are isopropylidene groups.

[6] The polycarbonate resin composition according to any one of [1] to [5], further comprising a polycarbonate resin having a structural unit represented by the following formula (3) in addition to the polycarbonate resin: .

(In formula (3), X has the same meaning as in formula (1).)

[7] The polycarbonate resin composition according to [6], wherein the content of the polycarbonate resin having the structural unit represented by the formula (3) is 90% by weight or less in the total polycarbonate resin.

[8] A molded article obtained by molding the polycarbonate resin composition according to any one of [1] to [7], and in a flame retardancy test of UL94 using a test piece having a thickness of 2 mm or less, V-0 A polycarbonate resin molded article characterized by satisfying the standard, having a haze value of 1.0 or less and a pencil hardness of HB or more by a test piece having a thickness of 3 mm based on JIS-K7136.

  According to the present invention, compared with the case of using a polycarbonate resin obtained by using bisphenol A or the like having no substituent as a monomer, the flame resistance is good while suppressing the decrease in the surface hardness and transparency of the molded body. A polycarbonate resin molded product can be obtained.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

<Polycarbonate resin composition>
(Polycarbonate resin)
Examples of the polycarbonate resin to which the present embodiment is applied include those containing at least a repeating unit represented by the following formula (1) in the molecule.

Here, in Formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and R ³ and R ⁴ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. ^{Incidentally,} the number of carbon atoms in ^{R 1, R 2, R 3} , R 4 indicates the number of carbon atoms of the alkyl group portion excluding the substituent.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ¹ and R ² include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -Butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. Examples of the substituted or unsubstituted aryl group include: A phenyl group, a benzyl group, a tolyl group, 4-methylphenyl group, a naphthyl group, etc. are mentioned.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ³ and R ⁴ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -Butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. Examples of the substituted or unsubstituted aryl group include: A phenyl group, a benzyl group, a tolyl group, 4-methylphenyl group, a naphthyl group, etc. are mentioned.

Among these, R ¹ and R ² are preferably a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a methyl group. R ³ and R ⁴ are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a hydrogen atom.

Here, the bonding positions of R ¹ , R ² , R ³ , and R ⁴ in formula (1) are arbitrary selected from the 2-position, 3-position, 5-position, and 6-position with respect to X on each phenyl ring. Position. Among these, the third and fifth positions are preferable.

In the formula (1), X represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom. Examples of the substituted or unsubstituted sulfur atom include —S— and —SO ₂ —. In addition, a substituted or unsubstituted alkylene group and a substituted or unsubstituted alkylidene group are shown below.

Here, R ⁵ and R ⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and Z is substituted or unsubstituted. A substituted alkylene group having 4 to 20 carbon atoms or a polymethylene group is shown. n represents an integer of 1 to 10.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ⁵ and R ⁶ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -Butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. Examples of the substituted or unsubstituted aryl group include a phenyl group, a benzyl group, a tolyl group, a 4-methylphenyl group, and a naphthyl group.
Among these, R ⁵ and R ⁶ are preferably a methyl group, an ethyl group, an n-propyl group, and a 4-methylphenyl group, more preferably a methyl group, and in particular, both R ⁵ and R ⁶ are methyl groups. And n is 1, that is, X in the formula (1) is preferably an isopropylidene group.

  Z is bonded to carbon bonding two phenyl groups in formula (1) to form a substituted or unsubstituted divalent carbocycle. Examples of the divalent carbocycle include a cycloalkylidene group such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group (preferably a carbon number of 5 To 8 carbon atoms. Examples of the substituted ones include those having these methyl substituents and ethyl substituents. Among these, a cyclohexylidene group and a methyl-substituted product of a cyclohexylidene group are preferable.

  The polycarbonate resin to which this exemplary embodiment is applied needs to contain at least a repeating unit represented by the formula (1). As a preferable range, the repeating unit of the formula (1) is 30% by weight or more, more preferably 40% by weight or more, and further preferably 50% by weight or more in the total aromatic diol structural unit. If the repeating unit of formula (1) is too small, the surface hardness and fluidity tend to be inferior.

Furthermore, the polycarbonate resin to which this embodiment is applied preferably satisfies the physical properties shown in the following (a) to (d).
(A) The intrinsic viscosity [η] (dl / g) at 20 ° C. in a methylene chloride solvent is in the range of 0.40 to 2.0. Further, the intrinsic viscosity [η] (dl / g) is preferably 0.50 to 1.00, particularly preferably 0.50 to 0.80. If the intrinsic viscosity [η] is excessively small, the mechanical strength tends to be inferior. If the intrinsic viscosity [η] is excessively large, the melt fluidity tends to deteriorate and the moldability tends to be inferior.

(B) The branch parameter G = [η] / [η] _lin is in the range of 0.1 to 0.9. Further, the branching parameter G is preferably 0.3 to 0.9, and particularly preferably 0.5 to 0.9. If the branching parameter G is excessively small, the melt tension tends to be too high and the fluidity tends to decrease. If the branching parameter G is excessively large, the melt behavior tends to be a Newtonian fluid and the moldability tends to be insufficient. is there.
Here, [η] _lin is an intrinsic viscosity at 20 ° C. in a methylene chloride solvent of a linear polycarbonate having the same weight average molecular weight measured by a light scattering method or a GPC method using a general calibration curve. In this embodiment, the viscosity equation is obtained from the intrinsic viscosity and the weight average molecular weight of a polycarbonate resin (linear polycarbonate) obtained by an interfacial polymerization method of an aromatic dihydroxy compound and carbonyl chloride without using a branching agent. , And a value calculated based on that.

In the present embodiment, the branch parameter G is calculated by the following method. That is, the branching parameter G of the polycarbonate resin is calculated by dividing the intrinsic viscosity [η] of the polycarbonate resin measured by the above-mentioned method by the intrinsic viscosity [η] _{lin of the} linear polycarbonate having the same weight average molecular weight. .
[Η] _lin measures the intrinsic viscosity of a polycarbonate resin produced by an interfacial polycondensation method without using a branching agent, and this is defined as the intrinsic viscosity [η] _lin of a linear polycarbonate. In addition, the weight average molecular weight (Mw) of the linear polycarbonate having the intrinsic viscosity [η] _lin is calculated from the molecular weight converted in advance to standard polystyrene obtained from the GPC measurement result of the polycarbonate resin, and the intrinsic viscosity [η]. -Viscosity relational expression is calculated and calculated from this molecular weight-viscosity relational expression.

(C) Using a capillary rheometer, logarithmic value lnη ^* ₁₀ of melt viscosity (Pa · s) measured at 300 ° C. under a shear rate of ₁₀ sec ⁻¹ is used as the intrinsic viscosity [η] at 20 ° C. in a methylene chloride solvent (η) ( The numerical value lnη ^* ₁₀ / [η] divided by dl / g) is 14.0 or less, and the logarithmic value lnη ^{* of} the melt viscosity (Pa · s) measured at 300 ° C. and a shear rate of 1000 sec ^{−1 .} _The numerical value lnη ^* ₁₀₀₀ / [η] obtained by dividing ₁₀₀₀ by the intrinsic viscosity [η] (dl / g) at 20 ° C. in a methylene chloride solvent is 11.0 or less.
These lnη ^* ₁₀ / [η] and lnη ^* ₁₀₀₀ / [η] preferably satisfy the above range at the same time. Outside the above range, the balance between fluidity and moldability tends to be impaired.
The lower limit of lnη ^* ₁₀ / [η] and lnη ^* ₁₀₀₀ / [η] is not particularly limited, but lnη ^* ₁₀ / [η] is more practically in the range of 11.0 to 14.0. Preferably, lnη ^* ₁₀₀₀ / [η] is more preferably in the range of 8.0 to 11.0.

Here, lnη ^* ₁₀ / [η] and lnη ^* ₁₀₀₀ / [η] mean an index indicating fluidity. For example, the melt viscosity may be different even for polycarbonate resins having the same intrinsic viscosity (= molecular weight). In order to reduce the thickness of the molded body, a material having good fluidity while maintaining mechanical strength is required. The mechanical strength needs to be adjusted so that the ratio of the melt viscosity to the intrinsic viscosity in the low shear rate range, that is, lnη ^* ₁₀ / [η] is within the above range. On the other hand, the fluidity needs to be adjusted so that the ratio of the melt viscosity to the extreme viscosity in the high shear rate region, that is, lnη ^* ₁₀₀₀ / [η] is within the above range.

In the present embodiment, lnη ^* ₁₀ / [η] and lnη ^* ₁₀₀₀ / [η] are calculated by the following method. That is, a polycarbonate resin dried at 100 ° C. for 5 hours was heated to 300 ° C. using a capillary rheometer (Capillograph C1 manufactured by Toyo Seiki Seisakusho Co., Ltd.) having a die diameter of 1 mmφ × 30 mmL, and a shear rate γ = 9.12− 1824 ^{(sec -1)} was measured between the ratio of the reading melt viscosity eta ^* ₁₀₀₀ in melt viscosity eta ^* ₁₀ and shear rate of 1,000 sec ^-1 at a shear rate of 10 sec ^-1, respectively, the intrinsic viscosity measured in advance [eta] ( lnη ^* ₁₀ / [η], lnη ^* ₁₀₀₀ / [η]).

(D) The pencil hardness according to JIS K5400 is HB or higher. Further, the pencil hardness of the polycarbonate resin is preferably F or more, more preferably H or more. However, it is usually 3H or less. A polycarbonate resin having a pencil hardness of less than HB tends to scratch the surface, and a conventional bisphenol A type polycarbonate resin has an insufficient pencil hardness of 2B.

  In the polycarbonate resin to which the present embodiment is applied, the ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn measured by gel permeation chromatography is 3.0 or more and 5.0. The following range is preferable. Further, (Mw / Mn) is more preferably within a range of 3.0 to 4.0. When (Mw / Mn) is too small, the fluidity in the molten state increases and the moldability tends to decrease. On the other hand, if (Mw / Mn) is excessively large, the melt viscosity tends to increase and molding tends to be difficult.

  The terminal hydroxyl group concentration of the polycarbonate resin to which this embodiment is applied is not particularly limited. In the case of the transesterification method, it is usually 100 ppm or more, preferably 200 ppm or more, and more preferably 300 ppm or more. However, it is usually 2000 ppm or less, preferably 1800 ppm or less, and more preferably 1200 ppm or less. If the terminal hydroxyl group concentration of the polycarbonate resin is excessively small, the initial hue of the molded product tends to deteriorate. When the terminal hydroxyl group concentration is excessively large, the residence heat stability tends to decrease.

<Production method of polycarbonate resin>
Next, a method for producing the polycarbonate resin used in the present embodiment will be described. Examples of the method for producing a polycarbonate resin include melt polycondensation (melting method) based on an ester exchange reaction between an aromatic dihydroxy compound and a carbonic acid diester, and an interfacial method based on interfacial polycondensation between an aromatic dihydroxy compound and carbonyl chloride. Among these, the melting method is preferable.

(Aromatic dihydroxy compounds)
The aromatic dihydroxy compound preferably contains an aromatic dihydroxy compound represented by the following formula (2) in both the melting method and the interface method.

In the formula (2), R ¹ , R ² , R ³ , R ⁴ and X have the same meanings as the formula (1).

  Specific examples of the aromatic dihydroxy compound represented by the formula (2) include 2,2-bis (3-methyl-4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4). -Hydroxyphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -3,5,5-trimethylcyclohexane, 1, 1-bis (4-hydroxy-3-methylphenyl) adamantane, 1,4-bis (4-hydroxy-3-methylphenyl) adamantane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 2 , 2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-cyclohexylphenyl) Lopan, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 5,5-bis (4-hydroxy-3-methylphenyl) hexahydro-4,7-methanoindane, 2,2-bis (4- Hydroxy-3-methylphenyl) sulfone, 2,2-bis (4-hydroxy-3-methylphenyl) sulfide, 3,3′-dimethylbiphenol, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) ) Propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylcyclohexane, , 1-bis (4-hydroxy-3,5-dimethylphenyl) adamantane, 1,4-bis (4-hydroxy-3,5-dimethylphenyl) Nyl) adamantane, 2,2-bis (3-ethyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propane, 2, 2-bis (3-cyclohexyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methyl-5-phenylphenyl) propane, 2,2-bis (3,5- Diethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-di-cyclohexyl-4-hydroxyphenyl) ) Propane, 2,2-bis (4-hydroxy-3,5-diphenylphenyl) propane, 5,5-bis (4-hydroxy-3,5-dimethylphenol) Nyl) hexahydro-4,7-methanoindane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) sulfone, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) sulfide, 3, 3 ′, 5,5′-tetramethylbiphenol and the like can be mentioned.

  Among these, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-) Methylphenyl) -3,5,5-trimethylcyclohexane, 5,5-bis (4-hydroxy-3-methylphenyl) hexahydro-4,7-methanoindane, 3,3′-dimethylbiphenol, 2,2-bis ( 4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl)- 3,5,5-trimethylcyclohexane, 5,5-bis (4-hydroxy-3,5-dimethylphenyl) hexahydro-4,7-me Noindan, 3,3 ', 5,5'-tetramethyl-biphenol, and the like.

Furthermore, among these, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, and 1,1-bis ( 4-hydroxy-3-methylphenyl) cyclohexane and 1,1-bis (4-hydroxy-3-methylphenyl) -3,5,5-trimethylcyclohexane are preferred, and 2,2-bis (3-methyl-4-) Hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, and 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane are preferred.
The aromatic dihydroxy compound represented by the formula (2) can be used alone or in combination of two or more. In the above formula (2), the preferred structures of R ¹ , R ² , R ³ , R ⁴ , and X and the preferred bonding position to the phenyl ring are the same as in formula (1).

(Melting method)
In the melting method, an aromatic dihydroxy compound and a carbonyl compound are used as raw materials, and a polycarbonate resin is produced by a melt polycondensation reaction that is continuously performed in the presence of a transesterification catalyst.

(Carbonyl compound)
Examples of the carbonyl compound used in the present embodiment include a carbonic acid diester compound represented by the following formula.

  Here, in the above formula, A ′ is a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. Two A's may be the same or different from each other. In addition, as a substituent on A ′, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, and an ester group Amide group, nitro group and the like.

Specific examples of the carbonic acid diester compound include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate.
Among these, diphenyl carbonate (hereinafter sometimes abbreviated as DPC) and substituted diphenyl carbonate are preferable. These carbonic acid diesters can be used alone or in admixture of two or more.

Moreover, the amount of the carbonic acid diester compound is preferably 50 mol% or less, more preferably 30 mol% or less, and may be substituted with dicarboxylic acid or dicarboxylic acid ester.
Typical dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, and the like. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

In the present embodiment, these carbonic acid diester compounds (including the above-mentioned substituted dicarboxylic acid or dicarboxylic acid ester; the same shall apply hereinafter) are used in excess with respect to the aromatic dihydroxy compound.
That is, with respect to the aromatic dihydroxy compound, the carbonic acid diester compound is usually used in a molar ratio of 1.01-1.30, preferably 1.02-1.20. When the molar ratio is excessively small, the terminal hydroxyl group concentration of the obtained polycarbonate resin becomes high, and the thermal stability tends to deteriorate. In addition, if the molar ratio is excessively large, the reaction rate of the transesterification decreases, and it becomes difficult to produce a polycarbonate resin having a desired molecular weight, and the residual amount of the carbonic diester compound in the resin increases. This is not preferable because it may cause an odor during molding or molding.

(Transesterification catalyst)
Examples of the transesterification catalyst used in the present embodiment include a catalyst that is usually used when producing a polycarbonate resin by a transesterification method, and is not particularly limited. In general, for example, basic compounds such as alkali metal compounds, alkaline earth metal compounds, beryllium compounds, magnesium compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds can be used. Among these, alkali metal compounds and alkaline earth metal compounds are desirable for practical use. These transesterification catalysts may be used alone or in combination of two or more.

The amount of the transesterification catalyst used is usually in the range of 1 × 10 ⁻⁹ to 1 × 10 ⁻¹ mol per 1 mol of the wholly aromatic dihydroxy compound, but an aromatic polycarbonate excellent in molding characteristics and hue is used. In order to obtain, the amount of the transesterification catalyst is preferably 1.0 × 10 ^{−6 to} 5 × with respect to 1 mol of the wholly aromatic dihydroxy compound when an alkali metal compound and / or an alkaline earth metal compound is used. It is in the range of 10 ⁻⁶ mol, more preferably in the range of 1.0 × 10 ⁻⁶ to 4 × 10 ⁻⁶ mol, particularly preferably 1.3 × 10 ^{−6 to} 3.8 × 10 ⁻⁶ mol. Is within the range. If the amount is less than the above lower limit, the amount of branching component that provides the polymerization activity and molding characteristics necessary for producing a polycarbonate having a desired molecular weight cannot be obtained. If the amount exceeds this amount, the polymer hue deteriorates and the amount of branching component Is too much, the fluidity is lowered, and an aromatic polycarbonate excellent in target molding characteristics cannot be produced.

Examples of the alkali metal compound include inorganic alkali metal compounds such as alkali metal hydroxides, carbonates and hydrogencarbonate compounds; organic alkali metal compounds such as salts with alkali metal alcohols, phenols and organic carboxylic acids. It is done. Here, as an alkali metal, lithium, sodium, potassium, rubidium, cesium etc. are mentioned, for example.
Among these alkali metal compounds, cesium compounds are preferable, and cesium carbonate, cesium hydrogen carbonate, and cesium hydroxide are particularly preferable.

Examples of the alkaline earth metal compound include inorganic alkaline earth metal compounds such as alkaline earth metal hydroxides and carbonates; alkaline earth metal alcohols, phenols, salts with organic carboxylic acids, and the like. It is done. Here, examples of the alkaline earth metal include calcium, strontium, barium and the like.
Examples of the beryllium compound and magnesium compound include inorganic metal compounds such as metal hydroxides and carbonates; salts of the metals with alcohols, phenols, and organic carboxylic acids.

  Examples of basic boron compounds include sodium salts, potassium salts, lithium salts, calcium salts, magnesium salts, barium salts, strontium salts, and the like of boron compounds. Here, as the boron compound, for example, tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributyl Examples include benzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and butyltriphenylboron.

  Examples of the basic phosphorus compound include trivalent phosphine compounds such as triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, and tributylphosphine, or derivatives thereof. And quaternary phosphonium salts.

  Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

  Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

(Manufacturing process of polycarbonate resin by melting method)
The production process of polycarbonate resin by the melting method is to prepare a raw material mixed melt of raw material aromatic dihydroxy compound and carbonic acid diester compound (original preparation process), and these compounds are melted in the presence of a transesterification reaction catalyst. It is carried out by performing a polycondensation reaction in multiple stages using a plurality of reactors (polycondensation step). The reaction system may be any of a batch system, a continuous system, or a combination of a batch system and a continuous system. As the reactor, a plurality of vertical stirring reactors and then at least one horizontal stirring reactor are used. Usually, these reactors are installed in series and processed continuously.
After the polycondensation process, the reaction is stopped, the unreacted raw materials and reaction byproducts in the polycondensation reaction liquid are devolatilized and removed, the process of adding a thermal stabilizer, mold release agent, colorant, etc. You may add suitably the process etc. which form in the pellet of a predetermined particle size.

(Interface method)
The method for producing a polycarbonate resin by the interfacial method usually involves preparing an alkaline aqueous solution of an aromatic dihydroxy compound, and performing an interfacial polycondensation reaction between the aromatic dihydroxy compound and carbonyl chloride in the presence of an amine compound used as a polymerization catalyst. Then, a polycarbonate resin is obtained through neutralization, water washing, and drying steps.

  Carbonyl chloride (hereinafter sometimes referred to as CDC) is usually used in liquid or gaseous form. The preferred amount of CDC used is appropriately selected depending on the reaction conditions, particularly the reaction temperature and the concentration of the metal salt of the aromatic dihydroxy compound in the aqueous phase, and is not particularly limited. Usually, CDC is 1 mol to 2 mol, preferably 1.05 mol to 1.5 mol, per 1 mol of the aromatic dihydroxy compound. When the amount of CDC used is excessively large, unreacted CDC increases and the basic unit tends to be extremely deteriorated. On the other hand, if the amount of CDC used is excessively small, the amount of chloroformate group is insufficient and proper molecular weight elongation tends not to be performed.

In the interface method, an organic solvent is usually used. Examples of the organic solvent include inert organic solvents that dissolve reaction products such as carbonyl chloride, carbonate oligomer, and polycarbonate resin and are incompatible with water (or do not form a solution with water).
Examples of such inert organic solvents include aliphatic hydrocarbons such as hexane and n-heptane; chlorinations such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, and 1,2-dichloroethylene. Aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; chlorinated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene and chlorotoluene; and other substituted aromatic hydrocarbons such as nitrobenzene and acetophenone It is done.
Among these, for example, chlorinated hydrocarbons such as dichloromethane or chlorobenzene are preferably used. These inert organic solvents can be used alone or as a mixture with other solvents.

  The condensation catalyst can be arbitrarily selected from many condensation catalysts used in the two-phase interfacial condensation method. For example, trialkylamine, N-ethylpyrrolidone, N-ethylpiperidine, N-ethylmorpholine, N-isopropylpiperidine, N-isopropylmorpholine and the like can be mentioned. Of these, triethylamine and N-ethylpiperidine are preferable.

  Monophenol is used as the chain terminator. Examples of monophenols include phenols; alkylphenols having 1 to 20 carbon atoms such as pt-butylphenol and p-cresol; halogenated phenols such as p-chlorophenol and 2,4,6-tribromophenol. Can be mentioned. The usage-amount of monophenol is suitably selected according to the molecular weight of the carbonate oligomer obtained, and is 0.5 mol%-10 mol% normally with respect to an aromatic dihydroxy compound.

In the interface method, the molecular weight of the polycarbonate resin is determined by the addition amount of a chain terminator such as monophenol. For this reason, from the viewpoint of controlling the molecular weight of the polycarbonate resin, the chain stopper is preferably added immediately after the consumption of the carbonate-forming compound is completed and before the molecular weight elongation starts.
When monophenol is added in the presence of a carbonate-forming compound, a large amount of condensates (diphenyl carbonates) of monophenols are produced, and it is difficult to obtain a polycarbonate resin having a target molecular weight. If the addition time of monophenol is extremely delayed, it becomes difficult to control the molecular weight, and furthermore, the resin has a specific shoulder on the low molecular weight side of the molecular weight distribution, and there is a tendency that problems such as dripping occur during molding.

  Moreover, arbitrary branching agents can be used for both the interface method and the melting method. Examples of such a branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane (THPE), 2,4-bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2- Hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, 1,4-bis (4,4′-dihydroxytriphenylmethyl) Examples include benzene. In addition, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and the like can also be used. Among these, a branching agent having at least three phenolic hydroxyl groups is preferable. The amount of the branching agent used is appropriately selected according to the degree of branching of the obtained carbonate oligomer, and is usually 0.05 mol% to 2 mol% with respect to the aromatic dihydroxy compound.

(Manufacturing process of polycarbonate resin by interface method)
The production process of the polycarbonate resin by the interfacial method involves preparing an alkaline aqueous solution of an aromatic dihydroxy compound (original preparation process), and performing a phosgenation reaction of the aromatic dihydroxy compound performed in the presence of carbonyl chloride (COCl ₂ ) and an organic solvent. Then, an oligomerization reaction of an aromatic dihydroxy compound is performed using a condensation catalyst and a chain terminator (oligomerization step), followed by a polycondensation reaction using an oligomer (polycondensation step), and after the polycondensation reaction The reaction solution is washed by alkali washing, acid washing, and water washing (washing process), the washed reaction liquid is pre-concentrated, and the polycarbonate resin is isolated after granulation (resin isolation process). This is done by drying the particles (drying process).

  In addition to the polycarbonate resin having the structural unit represented by the above-described formula (1), the polycarbonate resin used in the present embodiment may be a polycarbonate resin having a structural unit represented by the following formula (3) as necessary. Can be included.

Here, in the formula (3), X has the same meaning as the formula (1).
Specific examples of the polycarbonate resin having the structural unit represented by the formula (3) include, for example, a homopolymer of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), and the above-described formula (2). Examples include a copolymer of one or more of the aromatic dihydroxy compounds represented and bisphenol A.
In the present embodiment, when the polycarbonate resin having the structural unit represented by the formula (1) and the polycarbonate resin having the structural unit represented by the formula (3) are used in combination, the polycarbonate resin represented by the formula (3) is represented. The content of the polycarbonate resin having the structural unit is preferably 90% by weight or less in the total polycarbonate resin.

(Flame retardants)
The flame retardant used in the present embodiment is, for example, at least one selected from the group consisting of sulfonic acid metal salt flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants. Species are mentioned. Among these, a sulfonic acid metal salt flame retardant is preferable.
The amount of the flame retardant used in the present embodiment is usually 0.01 to 1 part by weight, preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the polycarbonate.

Examples of the sulfonic acid metal salt flame retardant include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts. Examples of the metal of these metal salts include sodium, lithium, potassium, rubidium and cesium alkali metals; beryllium and magnesium magnesium; and alkaline earth metals such as calcium, strontium and barium. A sulfonic acid metal salt can also be used 1 type or in mixture of 2 or more types.
Examples of the sulfonic acid metal salt include aromatic sulfonic acid metal salts and perfluoroalkane-sulfonic acid metal salts.

  Specific examples of the aromatic sulfonic acid metal salt include, for example, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, sodium 4,4′-dibromodiphenyl-sulfone-3-sulfonate, 4'-dibromodiphenyl-sulfone-3-sulfonic acid potassium, 4-chloro-4'-nitrodiphenyl sulfone-3-sulfonic acid calcium, diphenylsulfone-3,3'-disulfonic acid disodium, diphenylsulfone-3,3 Examples include dipotassium di-sulfonate.

  Specific examples of perfluoroalkane-sulfonic acid metal salt include perfluorobutane-sodium sulfonate, perfluorobutane-potassium sulfonate, perfluoromethylbutane-sodium sulfonate, perfluoromethylbutane-potassium sulfonate, perfluoro Examples include octane-sodium sulfonate, potassium perfluorooctane-sulfonate, and tetraethylammonium salt of perfluorobutane-sulfonic acid.

  Specific examples of the halogen-containing compound flame retardant include, for example, tetrabromobisphenol A, tribromophenol, brominated aromatic triazine, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A epoxy polymer, decabromodiphenyl oxide, tribromo Examples include allyl ether, tetrabromobisphenol A carbonate oligomer, ethylene bistetrabromophthalimide, decabromodiphenylethane, brominated polystyrene, hexabromocyclododecane and the like.

  Examples of the phosphorus-containing compound flame retardant include red phosphorus, coated red phosphorus, polyphosphate compound, phosphate ester compound, and phosphazene compound. Among these, specific examples of the phosphate ester compound include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl. Phosphate, diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3- Dibromopropyl) phosphate, bis (chloropropyl) monooctyl phosphate, bisphenol A bisphosphate, hydro Non bisphosphate, resorcinol bisphosphate, trioxybenzene phosphate.

  Examples of the silicon-containing compound flame retardant include silicone varnish, a silicone resin in which a substituent bonded to a silicon atom is an aromatic hydrocarbon group and an aliphatic hydrocarbon group having 2 or more carbon atoms, and a main chain having a branched structure. And a silicone compound having an aromatic group in the organic functional group contained therein, a silicone powder carrying a polydiorganosiloxane polymer which may have a functional group on the surface of the silica powder, and an organopolysiloxane-polycarbonate copolymer Etc.

  The polycarbonate resin composition to which the present embodiment is applied is, for example, a polycarbonate resin obtained by using bisphenol A as a raw material monomer by combining a polycarbonate resin having a structural unit represented by the above formula (1) and a flame retardant. Compared with a resin composition using (A-PC), flame retardancy is improved.

  Although the reason why the flame retardancy of the polycarbonate resin composition to which the present embodiment is applied is not clear, for example, the polycarbonate resin component includes 2,2-bis (3-methyl-4-) of an aromatic dihydroxy compound. Taking the case of using a polycarbonate resin (referred to as “C-PC”) obtained by using hydroxyphenyl) propane as a raw material monomer, it is considered as follows.

  That is, C-PC has a lower thermal decomposition starting temperature than A-PC and may be easily decomposed. For this reason, C-PC is easily decomposed and graphitized, and easily exhibits flame retardancy by forming a heat insulating layer (char). The thermal decomposition initiation temperature of C-PC is lower than that of A-PC because of the structural difference that “the 3-position of two benzene rings is substituted with a methyl group” of the bisphenol skeleton. Yes. In particular, when C-PC is produced by the above-described melting method, when the polymerization reaction proceeds in a molten state at a high temperature and under a high shearing force, a branched chain tends to be generated from the 3-position of both phenyl rings of the bisphenol compound. For this reason, it is considered that flame retardancy such as suppression of combustion drops (drip) is improved in the combustion test.

Furthermore, C-PC has a lower packing density between molecular chains than A-PC, and since the molecular chains are rigid and difficult to move, the shrinkage rate of the resin molded product tends to be low and the linear expansion coefficient tends to be low. is there. For this reason, it is expected that the dimensional stability of the resin molded product is high.
Since the polycarbonate resin composition to which this embodiment is applied has such characteristics, for example, a casing for precision equipment such as a mobile phone and a PC; a housing for home appliances such as a TV; a film for a screen; Suitable for resin members that require high dimensional accuracy, such as multi-layer molded resin molded products of two or more colors, such as carports, agricultural houses, soundproof boards, and other multilayer extruded products with two or more surface layers. is there.
In addition, the polycarbonate resin composition to which the present embodiment is applied can obtain a resin molded body having high hardness and improved flame retardancy, and thus, for example, illumination related resins such as LEDs such as a lamp lens, a protective cover, and a diffusion plate Molded article; suitable for uses such as glasses lenses, vending machine buttons, keys for portable devices, and the like.

Various additives are blended in the polycarbonate resin composition to which the present embodiment is applied, if necessary. Examples of additives include stabilizers, ultraviolet absorbers, mold release agents, colorants, antistatic agents, thermoplastic resins, thermoplastic elastomers, glass fibers, glass flakes, glass beads, carbon fibers, wollastonite, silicic acid. Examples thereof include calcium and aluminum borate whiskers.
There are no particular limitations on the method of mixing the polycarbonate resin, the flame retardant, and the additives blended as necessary. In the present embodiment, for example, after mixing a solid state polycarbonate resin such as pellets or powder and a flame retardant, etc., a method of kneading with an extruder or the like, a method of mixing a molten state polycarbonate resin and a flame retardant, etc., melting The method of adding a flame retardant etc. in the middle of the polymerization reaction of the raw material monomer in the method or the interfacial method or at the end of the polymerization reaction, etc. may be mentioned.

<Polycarbonate resin molding>
A polycarbonate resin molded body is prepared using the polycarbonate resin composition to which the above-described embodiment is applied. The molding method of the polycarbonate resin molding is not particularly limited, and examples thereof include a molding method using a conventionally known molding machine such as an injection molding machine.
The polycarbonate resin molded body to which this embodiment is applied is, for example, compared with the case where a polycarbonate resin obtained using bisphenol A or the like having no substituent on the phenyl ring as a monomer is used, and the surface hardness and transparency of the molded body. The deterioration of the property is suppressed, and the flame retardancy is good.
Specifically, the polycarbonate resin molded body to which the present embodiment is applied preferably satisfies the V-0 standard in the flame retardancy test of UL94 using a test piece having a thickness of 2 mm or less. About transparency, it is preferable that the haze value by the test piece of thickness 3mm based on prescription | regulation of JIS-K7136 is 1.0 or less.

  Hereinafter, the present invention will be described more specifically based on examples. In addition, this invention is not limited to a following example, unless it deviates from the summary.

(I) Polycarbonate resin composition A. Polycarbonate resin (1) Polycarbonate resin having repeating unit represented by formula (1) in the molecule (i) Preparation of polycarbonate resin (PC-1) by melting method 2,2-bis (3-methyl-4-hydroxy (Phenyl) propane (hereinafter referred to as “BPC”) 6.59 mol (1.69 kg) and diphenyl carbonate 6.73 mol (1.44 kg) were added to a SUS reactor equipped with a stirrer and a distillation condenser. (Internal volume 10 liters), the inside of the reactor was replaced with nitrogen gas, and then heated to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is used as a transesterification reaction catalyst in the molten reaction solution so that the amount becomes 1.5 × 10 ⁻⁶ mol per 1 mol of BPC. In addition (3.20 mg as Cs ₂ CO ₃ ), the reaction solution was stirred and brewed at 220 ° C. for 30 minutes under a nitrogen gas atmosphere. Next, under the same temperature, the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further performed for 100 minutes to distill phenol.

Next, the temperature in the reactor was raised to 284 ° C. over 60 minutes and the pressure was reduced to 3 Torr, and phenol corresponding to almost the entire distillation amount was distilled. Next, the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was further continued for 60 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 16 rotations / minute, the reaction liquid temperature immediately before the completion of the reaction was 300 ° C., and the stirring power was 1.15 kW.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4-fold molar amount of butyl p-toluenesulfonate is supplied from the first supply port of the twin screw extruder with respect to cesium carbonate, After kneading with the reaction solution, the reaction solution was extruded in a strand shape through a die of a twin screw extruder and cut with a cutter to obtain carbonate resin pellets.

In addition, the physical property of the obtained polycarbonate resin (PC-1) is shown below.
Intrinsic viscosity [η] (dl / g) 0.708
Branch parameter G ([η] / [η] _lin ) 0.83
lnη ^* ₁₀ / [η] 11.6
lnη ^* ₁₀₀₀ / [η] 8.6
η ^* ₁₀ / η ^* ₁₀₀₀ 7.9
Pencil hardness 2H
Weight average molecular weight (Mw) 99,500
(Mw / Mn) 3.94

(Ii) Preparation of polycarbonate resin (PC-2) by interfacial method BPC 13.80 kg / hr, sodium hydroxide (NaOH) 5.8 kg / hr and water 93.5 kg / hr, hydrosulfite 0.017 kg / hr In the presence, after dissolving at 35 ° C., an aqueous phase cooled to 25 ° C. and an organic phase of 61.9 kg / h of methylene chloride cooled to 5 ° C. were each Teflon (registered trademark) having an inner diameter of 6 mm and an outer diameter of 8 mm. In a pipe reactor made of Teflon (registered trademark) having an inner diameter of 6 mm and a length of 34 m connected to this pipe, it was brought into contact with 7.2 kg / hour of liquefied phosgene cooled to 0 ° C. separately introduced here.

  The raw material is subjected to phosgenation and oligomerization reaction while flowing through phosgene and a pipe reactor at a linear velocity of 1.7 m / second for 20 seconds. At this time, the reaction temperature reached a tower top temperature of 60 ° C. in the heat insulation system. The temperature of the reaction product was adjusted by external cooling to 35 ° C. before entering the next oligomerization tank.

In the oligomerization, triethylamine 5 g / hour (0.9 × 10 ⁻³ mole relative to 1 mole of BPC) was used as a catalyst, and pt-butylphenol 0.153 kg / hour was used as a molecular weight regulator. Introduced.

In this way, the oligomerized emulsion obtained from the pipe reactor is further guided to a reaction tank with a stirrer having an internal volume of 50 liters, and stirred at 30 ° C. in a nitrogen gas (N ₂ ) atmosphere to be oligomerized. Thus, after consuming unreacted BPC sodium salt (BPC-Na) present in the aqueous phase, the aqueous phase and the oil phase were allowed to stand and separate to obtain an oligomeric methylene chloride solution.

Of the above methylene chloride solution of oligomer, 23 kg was charged into a reaction vessel equipped with a 70 liter Faudler vane, and 10 kg of methylene chloride for dilution was added thereto. Further, 2.2 kg of 25 wt% aqueous sodium hydroxide solution and 6 kg of water were added. And 2.2 g of triethylamine (1.1 × 10 ⁻³ mol relative to 1 mol of BPC) were added, and the mixture was stirred at 30 ° C. in a nitrogen gas atmosphere and subjected to a polycondensation reaction for 60 minutes to obtain a polycarbonate resin.

  Next, 30 kg of methylene chloride and 7 kg of water were added, and after stirring for 20 minutes, stirring was stopped and the aqueous phase and the organic phase were separated. To the separated organic phase, 20 kg of 0.1N hydrochloric acid was added and stirred for 15 minutes to extract triethylamine and a small amount of remaining alkali component, and then stirring was stopped to separate the aqueous phase and the organic phase.

  Further, 20 kg of pure water was added to the separated organic phase, and the mixture was stirred for 15 minutes, and then the stirring was stopped to separate the aqueous phase and the organic phase. This operation was repeated (three times) until no chlorine ions were detected in the extracted waste water. The obtained purified polycarbonate solution was pulverized by feeding into warm water at 40 ° C., and dried to obtain a granular powder of polycarbonate resin.

The obtained polycarbonate resin flakes were fed into a twin screw extruder, extruded through a die of the twin screw extruder into a strand, and cut with a cutter to obtain polycarbonate resin pellets. The physical properties of the obtained polycarbonate resin (PC-2) are shown below.
Intrinsic viscosity [η] (dl / g) 0.661
Branch parameter G ([η] / [η] _lin ) 1.00
lnη ^* ₁₀ / [η] 11.3
lnη ^* ₁₀₀₀ / [η] 9.1
η ^* ₁₀ / η ^* ₁₀₀₀ 3.8
Pencil hardness 2H
Weight average molecular weight (Mw) 89,800
(Mw / Mn) 3.55

(2) Other polycarbonate resin <PC-3>: Novalex M7027BF manufactured by Mitsubishi Engineering Plastics Co., Ltd.
Intrinsic viscosity [η] (dl / g) 0.559
Branch parameter G ([η] / [η] _lin ) 0.88
lnη ^* ₁₀ / [η] 14.5
lnη ^* ₁₀₀₀ / [η] 11.4
η ^* ₁₀ / η ^* ₁₀₀₀ 5.7
Pencil hardness 2B
(Mw / Mn) 2.70
<PC-4>: Iupilon E-2000 intrinsic viscosity [η] (dl / g) 0.586 manufactured by Mitsubishi Engineering Plastics Co., Ltd.
Branch parameter G ([η] / [η] _lin ) 1.00
lnη ^* ₁₀ / [η] 15.1
lnη ^* ₁₀₀₀ / [η] 11.2
η ^* ₁₀ / η ^* ₁₀₀₀ 9.8
Pencil hardness 2B
(Mw / Mn) 3.10
<PC-5>: In the preparation of the polycarbonate resin (PC-1) described above, 0.83 kg of BPA and 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (hereinafter referred to as “Bis-OCZ” instead of BPC) The same operation was carried out except that 0.83 kg was used and Cs ₂ CO ₃ was changed to 5.0 × 10 ⁻⁶ mol with respect to 1 mol of all bisphenols to obtain a polycarbonate resin (PC-5). It was. As a result of measuring the obtained polycarbonate resin (PC-5) by ¹ H-NMR, the BPA carbonate part was 50.2% by mass, and the Bis-OCZ carbonate part was 49.8% by mass. The physical properties of the obtained polycarbonate resin (PC-5) are shown below.
Intrinsic viscosity [η] (dl / g) 0.468
Branch parameter G ([η] / [η] _lin ) 0.88
lnη ^* ₁₀ / [η] 15.6
lnη ^* ₁₀₀₀ / [η] 13.0
η ^* ₁₀ / η ^* ₁₀₀₀ 9.8
Pencil hardness 2H
Weight average molecular weight (Mw) 50,300
(Mw / Mn) 2.75

B. Flame retardant metal sulfonate flame retardant: Perfluorobutane sulfonate potassium salt (Biowet C4 manufactured by Bayer Co., Ltd.)
Sulfonic acid metal salt flame retardant: Perfluorobutanesulfonic acid potassium salt (F114P manufactured by Bayer Co.)
Phosphorus-containing compound-based flame retardant PX200: aromatic condensed phosphate ester-based flame retardant (PX200 manufactured by Daihachi Chemical Co., Ltd.)
Phosphorus-containing compound flame retardant FP110: Phosphazene derivative flame retardant (FP110 manufactured by Fushimi Pharmaceutical Co., Ltd.)
Halogen-containing compound flame retardant FR53: Brominated polycarbonate resin flame retardant (Iupilon FR FR53 manufactured by Mitsubishi Engineering Plastics)

C. Mold release agent pentaerythritol tetrastearate (Unistar H-476 manufactured by NOF Corporation)

(II) Test of polycarbonate resin composition Flammability test Using a polycarbonate resin composition, the thickness varies according to the UL standard on an injection molding machine (SG75-Cycap MII manufactured by Sumitomo Heavy Industries, Ltd.) under conditions of a cylinder temperature of 280 ° C. and a molding cycle of 1 minute. A plurality of test pieces were injection molded, and a UL standard 94 20 mm vertical combustion test was conducted. In the UL class, “V-0” means V-0 pass, “V-2” means V-2 pass, and “V-2NG” means V-2 fail.
Here, V-0, V-1, and V-2 are all determined using five test pieces. Specifically, a burner flame is applied to the lower end of the vertically-supported strip-shaped test piece and kept for 10 seconds, and then the burner flame is separated from the test piece. Release the flame.

The determination of V-0, V-1, and V-2 is the flaming combustion duration after the first and second flame contact ends, the flammable combustion duration and the flameless combustion duration after the second flame termination. It is determined by the total time, the total flammable combustion duration of the five test pieces, and the presence or absence of combustion drops (drip).
In both the first time and the second time, V-0 is determined within 10 seconds, and V-1 and V-2 are determined based on whether or not the flammable combustion is completed within 30 seconds. Further, the sum of the second flammable combustion duration and the flameless combustion duration is determined based on whether V-0 disappears within 30 seconds and V-1 and V-2 disappear within 60 seconds.
Furthermore, the total of the flammable combustion durations of the five test pieces is determined based on whether V-0 is within 50 seconds and V-1 and V-2 are within 250 seconds. Moreover, combustion fallen objects are allowed only for V-2. All specimens must not burn out.

B. Pencil hardness A plate of polycarbonate resin composition having a thickness of 3 mm, a length of 100 mm, and a width of 100 mm under conditions of a barrel temperature of 280 ° C. and a mold temperature of 90 ° C. using an injection molding machine (J100SS-2 manufactured by Nippon Steel) Was injection molded. About the plate obtained by this injection molding, the pencil hardness was measured under a load of 750 g using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with ISO15184.

C. Haze test (transparency)
A test piece having a thickness of 3 mm was molded according to JIS K-7136 using the polycarbonate resin composition. Using a haze meter (NDH-2000 model manufactured by Nippon Denshoku Industries Co., Ltd.), the haze in the molded products molded at molding temperatures of 280 ° C., 300 ° C., and 320 ° C. was measured.

(Examples 1-4, Reference Examples 1-3, Comparative Examples 1-3)
Using the polycarbonate resin (PC-1) prepared by the melting method described above, other polycarbonate resins (PC-3, PC-4), flame retardants and mold release agents, these are shown in Table 1 (weight ratios are shown). The same applies to the following tables.) And kneaded at a barrel temperature of 280 ° C. with a twin-screw extruder (TEX30HSST manufactured by Nippon Steel Works) to prepare a polycarbonate resin composition. The obtained pellets were dried at 120 ° C. for 5 hours, and then various test pieces were prepared according to the above procedure, and the combustibility, pencil hardness, and transparency were measured. The results are shown in Table 1.

From the results shown in Table 1, resin molded bodies obtained from polycarbonate resin compositions containing a polycarbonate resin having a repeating unit represented by the formula (1) in the molecule and a flame retardant (Examples 1 to 4 ) Compared to the case of using a polycarbonate resin obtained by using bisphenol A or the like having no substituent as a monomer (Comparative Example 1, Comparative Example 2), while suppressing the decrease in surface hardness and transparency of the molded product, It can be seen that a polycarbonate resin molded article having good flame retardancy can be obtained.

(Example 5, Reference Examples 4 , 5 and Comparative Example 4)
Except for using the polycarbonate resin (PC-2) and other polycarbonate resin (PC-5) prepared by the interface method described above, the polycarbonate resin composition was prepared in the same manner as in Example 1 with the composition shown in Table 2. The combustibility, pencil hardness, and transparency of each of the prepared and created test pieces were measured. The results are shown in Table 2.

From the results shown in Table 2, resin molded bodies obtained from polycarbonate resin compositions containing a polycarbonate resin having a repeating unit represented by the formula (1) in the molecule obtained by the interface method and a flame retardant (Examples) 5 ) shows that the fall of transparency is further suppressed compared with the polycarbonate resin composition (Examples 1-4 ) containing the polycarbonate resin obtained by the melting method.

( Reference Examples 6 to 10 and Comparative Example 5)
(Preparation of polycarbonate resin (PC-6))
In the preparation of the polycarbonate resin (PC-1) described above, BPA was changed to 100% and 0.34 kg of BPA and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane (abbreviated as Tm-BPA) 1 .34 kg was used together, Cs ₂ CO ₃ was changed to 5.0 × 10 ⁻⁶ mol relative to 1 mol of the total amount of BPA and Tm-BPA, and THPE was changed to 1 mol of the total amount of BPA and Tm-BPA. A polycarbonate resin (PC-6) was produced under the same conditions except that 3.5 × 10 ⁻³ mol was added. As a result of ¹ H-NMR measurement of the polycarbonate resin (PC-6), the BPA carbonate part in the resin was 20.4% by mass and the Tm-BPA carbonate part was 79.6% by mass.

In addition, the physical property of the obtained polycarbonate resin (PC-6) is shown below.
Intrinsic viscosity [η] (dl / g) 0.512
Branch parameter G ([η] / [η] _lin ) 0.90
lnη ^* ₁₀ / [η] 13.3
lnη ^* ₁₀₀₀ / [η] 10.1
η ^* ₁₀ / η ^* ₁₀₀₀ 5.1
Pencil hardness H
Weight average molecular weight (Mw) 61,300
(Mw / Mn) 3.21

  Next, using the above-described polycarbonate resin (PC-6), other polycarbonate resins (PC-3, PC-7), flame retardant and release agent, these are blended and mixed in the composition shown in Table 3, and biaxial. A polycarbonate resin composition was prepared by kneading at an barrel temperature of 280 ° C. with an extruder (TEX30HSST manufactured by Nippon Steel Works). The obtained pellets were dried at 120 ° C. for 5 hours, and then various test pieces were prepared according to the procedure described above, and the flammability, pencil hardness, load deflection temperature (DTUL), and transparency were measured. The results are shown in Table 3.

Other polycarbonate resins (PC-7) are as follows.
Polycarbonate resin (PC-7): Iupilon S-3000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.
Intrinsic viscosity [η] (dl / g) 0.475
Branch parameter G ([η] / [η] _lin ) 1.0
lnη ^* ₁₀ / [η] 14.3
lnη ^* ₁₀₀₀ / [η] 12.4
η ^* ₁₀ / η ^* ₁₀₀₀ 2.5
Pencil hardness 2B
Weight average molecular weight (Mw) 45,000
(Mw / Mn) 2.90

<Load deflection temperature (DTUL)>
After the pellets of the polycarbonate resin composition shown in Table 3 were dried for 3 hours using a dryer at 100 ° C., the injection speed was 200 mm / second, the holding pressure was 70 MPa, using an injection molding machine (IS-80EPN manufactured by Toshiba Machine Co., Ltd.). (Injection + holding pressure) Time 20 seconds, cooling time 20 seconds, mold temperature 120 ° C., molten resin temperature 330 ° C. were set, and a multi-purpose test piece A-type molded piece conforming to ISO 3167 was molded. Using a test piece of 80 mm × 10 mm × 4 mm cut out from the obtained molded piece, a deflection temperature under a load of 1.80 MPa was measured by a flatwise method in accordance with ISO75 (DTUL: unit ° C.). The larger the value, the better the heat resistance.

From the results shown in Table 3, it is obtained using 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane among polycarbonate resins having a repeating unit represented by the formula (1) in the molecule. It turns out that the molded object which improved heat resistance is obtained by the composition ( Reference Examples 6-10 ) which mix | blended the obtained polycarbonate resin and a flame retardant.

(Preparation of polycarbonate resin (PC-8))
An aqueous solution of cesium carbonate was added to 37.6 kg (about 147 mol) of BPC (Honshu Chemical Co., Ltd.) and 32.2 kg (about 150 mol) of diphenyl carbonate (DPC) so that the cesium carbonate was 2 μmol per mol of BPC. Adjusted. Next, the mixture was charged into a first reactor having an internal volume of 200 L equipped with a stirrer, a heat medium jacket, a vacuum pump, and a reflux condenser.

  Next, the operation of depressurizing the inside of the first reactor to 1.33 kPa (10 Torr) and then restoring the pressure to the atmospheric pressure with nitrogen was repeated five times to replace the inside of the first reactor with nitrogen. After nitrogen substitution, the internal temperature of the first reactor was gradually raised through a heat medium having a temperature of 230 ° C. through the heat medium jacket to dissolve the mixture. Then, the stirrer was rotated at 300 rpm, the temperature in the heating medium jacket was controlled, and the internal temperature of the first reactor was kept at 220 ° C. The pressure in the first reactor was 101.3 kPa (760 Torr) in absolute pressure over 40 minutes while distilling off phenol produced as a by-product by the oligomerization reaction of BPC and DPC performed in the first reactor. To 13.3 kPa (100 Torr).

  Subsequently, a transesterification reaction was performed for 80 minutes while maintaining the pressure in the first reactor at 13.3 kPa and further distilling off the phenol. The inside of the system was restored to absolute pressure of 101.3 kPa with nitrogen, the gauge pressure was increased to 0.2 MPa, and the oligomer in the first reactor was passed through a transfer pipe heated to 200 ° C. or higher in advance. Two reactors were pumped. The second reactor had an internal volume of 200 L and was equipped with a stirrer, a heat medium jacket, a vacuum pump and a reflux condenser, and the internal pressure was controlled to atmospheric pressure and the internal temperature was controlled to 240 ° C.

  Next, the oligomer fed into the second reactor was stirred at 38 rpm, the internal temperature was raised with a heat medium jacket, and the inside of the second reactor was absolute pressure from 101.3 kPa to 13.3 kPa over 40 minutes. The pressure was reduced to. Thereafter, the temperature increase was continued, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) as an absolute pressure over an additional 40 minutes, and phenol distilled out was removed out of the system. Further, the temperature was continuously raised, and after the absolute pressure in the second reactor reached 70 Pa (about 0.5 Torr), the pressure was maintained at 70 Pa, and a polycondensation reaction was performed. The final internal temperature in the second reactor was 285 ° C.

  The polycondensation reaction was terminated when the stirrer of the second reactor reached a predetermined stirring power. At this time, the stirring rotation speed of the stirrer was 6 rotations / minute, the reaction liquid temperature immediately before the completion of the reaction was 282 ° C., and the stirring power was 1.27 kW.

Next, the inside of the second reactor is restored to 101.3 kPa in absolute pressure with nitrogen, and the gauge pressure is increased to 0.2 MPa, and the polycarbonate resin is extracted in a strand form from the bottom of the second reactor, The mixture was pelletized by using a rotary cutter while being cooled at the same time. The physical properties of the obtained polycarbonate resin (PC-8) are shown below.
Intrinsic viscosity [η] (dl / g) 0.700
Branch parameter G ([η] / [η] _lin ) 0.82
lnη ^* ₁₀ / [η] 11.2
lnη ^* ₁₀₀₀ / [η] 8.7
η ^* ₁₀ / η ^* ₁₀₀₀ 5.8
Pencil hardness 2H

(Polycarbonate resin (PC-9)): Novalex 7030PJ manufactured by Mitsubishi Engineering Plastics Co., Ltd.
Intrinsic viscosity [η] (dl / g) 0.640
Branch parameter G ([η] / [η] _lin ) 1.00
Pencil hardness 2B

( Reference Examples 11 and 12 and Comparative Example 6)
Using the polycarbonate resin (PC-8) prepared by the above-mentioned melting method, other polycarbonate resin (PC-9), and a flame retardant, these were blended and mixed with the composition shown in Table 4, and a twin-screw extruder (Nippon Steel Works). KEX at a barrel temperature of 280 [deg.] C. to prepare a polycarbonate resin composition. The obtained pellets were dried at 120 ° C. for 5 hours, and then various test pieces were prepared according to the procedure described above, and the flammability, pencil hardness, and transparency were measured. The results are shown in Table 4.

  From the results shown in Table 4, a composition containing a specific polycarbonate resin and a flame retardant can be used to obtain a good molded article having improved flame retardancy and high hardness while maintaining the color tone. I understand.

Claims (5)

A polycarbonate resin having a structural unit represented by the following formula (1) in the molecule;
And a sulfonic acid metal salt-based flame retardant, only including,
Content of the polycarbonate resin which has a structural unit represented by Formula (1) is 50 weight% or more in all the polycarbonate resins, The polycarbonate resin composition characterized by the above-mentioned .

(In Formula (1), R ¹ and R ² each independently represent a methyl group bonded to the 3-position carbon of the phenyl group. R ³ and R ⁴ each independently represents the 5-position of the phenyl group. And represents a hydrogen atom bonded to carbon, and X represents an isopropylidene group . The polycarbonate resin composition according to claim 1, comprising 0.05 part by weight to 1 part by weight of the sulfonic acid metal salt-based flame retardant with respect to 100 parts by weight of the total polycarbonate resin. In addition to the polycarbonate resin having a structural unit represented by the formula (1), further, according to claim 1 or 2, characterized in that it comprises a polycarbonate resin having a structural unit represented by the following formula (3) Polycarbonate resin composition.

(In formula (3), X has the same meaning as in formula (1).) The polycarbonate resin composition according to claim 3 , wherein the content of the polycarbonate resin having the structural unit represented by the formula (3) is 50 % by weight or less based on the total polycarbonate resin. A molded body formed by molding the polycarbonate resin composition according to any one of claims 1 to 4 , which satisfies the V-0 standard in a flame retardant test of UL94 using a test piece having a thickness of 2 mm or less, A polycarbonate resin molded article having a haze value of 1.0 or less and a pencil hardness of HB or more according to a test piece having a thickness of 3 mm based on JIS-K7136.