JP2003238792A - Polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition which is transparent, highly flowable, and excellent in the balance between flowability and impact resistance. <P>SOLUTION: This polycarbonate resin composition comprises a linear polycarbonate resin the molecular end of which is a monoalkylphenol and of which the mean number of carbon atoms of alkyl groups is 8-17 and a linear polycarbonate resin the molecular end of which is p-tert-butylphenol. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a terminal p-ter.
Physical properties such as impact resistance and transparency are equivalent to polycarbonate resin which is t-butylphenol (PTBP),
Fluidity (S
The present invention relates to a linear polycarbonate resin composition having an excellent balance between FL) and impact resistance.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in mechanical properties (especially impact resistance), electrical properties, transparency, etc.
It is widely used in various fields such as equipment, electric and electronic equipment, and construction.

In recent years, it has become necessary to further improve the fluidity in order to meet the demand for thinner and larger molded products and improved molding cycle. To improve its flowability, it is known to use long-chain alkylphenols as endcappers. For example, the claims of Japanese Examined Patent Publication (Kokoku) No. 52-50078 describe that an alkylphenol having an alkyl group having 8 to 20 carbon atoms, a carboxylic acid or an acid halide is used as a terminal terminating agent. However,
In the examples, there is only description of an acid chloride having an alkyl group having 9 to 17 carbon atoms, and when the carbon number exceeds 20, the system becomes emulsified when the polymer solution is washed with water, which makes cleaning difficult.
There is a problem that the heat distortion temperature of the obtained polycarbonate resin is significantly lowered. Japanese Patent Publication No. 7-25871 discloses an alkylphenol-terminated polycarbonate resin having 8 to 30 carbon atoms. However, although this alkylphenol-terminated polycarbonate resin has excellent transparency and fluidity, its impact resistance is extremely low.

[0004]

The present invention has been made under such circumstances, and is a straight-chain polycarbonate which is transparent, has a high fluidity, and has a good balance between fluidity (SFL) and impact resistance. The present invention relates to a resin composition.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that a linear polycarbonate resin having a long-chain monoalkylphenol at the end and a linear polycarbonate resin having a PTBP at the end. When blended with polycarbonate resin, it is transparent and has high fluidity and fluidity (SFL).
It was found that a polycarbonate resin composition having a good balance between the impact resistance and the impact resistance can be obtained. The present invention has been completed based on such findings.

That is, according to the present invention, a linear polycarbonate resin having a monoalkylphenol terminal and an alkyl group having an average carbon number of 8 to 17 and a terminal p-tert.
-It relates to a polycarbonate resin composition comprising a linear polycarbonate resin which is butylphenol.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. In the polycarbonate resin composition of the present invention, the content of the linear polycarbonate resin in which the terminal is an alkyl group having an average carbon number of 8 to 17 is a monoalkylphenol, is preferably 20 to 80% by mass, and more preferably 25. Is about 75% by mass. Furthermore, it is preferably 50 to 70 mass%. When the content of the linear polycarbonate resin having an alkyl group at the end of which is a monoalkylphenol having an average carbon number of 8 to 17 is less than 20% by mass, the impact resistance is maintained but the fluidity is not improved. When the content of the linear polycarbonate resin which is a monoalkylphenol having an alkyl group having an average carbon number of 8 to 17 at the end exceeds 80% by mass, the fluidity is improved, but the impact resistance at 0 ° C is a brittle fracture region. Falls to. Further, the content of the linear polycarbonate resin having a terminal of p-tert-butylphenol of the polycarbonate resin composition of the present invention is 8
It is 0 to 20% by mass, preferably 75 to 20% by mass. Furthermore, it is preferably 50 to 30 mass%. When the content of the linear polycarbonate resin having a terminal of p-tert-butylphenol is less than 20% by mass, the fluidity is improved, but the impact resistance at 0 ° C is reduced to the brittle fracture region. When the content of the linear polycarbonate resin having a terminal of p-tert-butylphenol exceeds 80% by mass, the impact resistance is maintained but the fluidity is not improved.

As the linear polycarbonate resin of the present invention, various ones can be mentioned.

[0009]

[Chemical 1]

A compound having a repeating unit of the structure
Coalescence is preferred. In the general formula (I), X¹Over
And X²Are linear, branched or C1-C6, respectively.
A cyclic alkyl group is shown, and specific examples include a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl
Group, isobutyl group, tert-butyl group, n-amyl group
Group, isoamyl group, n-hexyl group, isohexyl group,
Include cyclopentyl group, cyclohexyl group, etc.
You can This X¹And X²Are the same but different
It may be. a and b are each X¹And X²
Is an integer of 0 to 4. X ¹There are multiple
If multiple X¹May be the same or different from each other
X²If there are multiple²Are the same as each other
It may be different.

Y is a single bond, an alkylene group having 1 to 8 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, pentylylene group and hexylene group), an alkylidene group having 2 to 8 carbon atoms (for example, ethylidene group). Groups and isopropylidene groups, etc.), cycloalkylene groups having 5 to 15 carbon atoms (eg, cyclopentylene group and cyclohexylene group, etc.), cycloalkylidene groups having 5 to 15 carbon atoms (eg, cyclopentylidene group and cyclohexylidene group) Den group), - S -, - SO -, - SO 2 -, - O -, -
CO-bond, formula (II-1) or formula (II-2)

[0012]

[Chemical 2]

The bond represented by The polymer is usually represented by the general formula (III)

[0014]

[Chemical 3]

The dihydric phenol represented by the formula (wherein X ¹ , X ² , a, b and Y are the same as above) is reacted with a carbonate precursor such as phosgene or a carbonate compound. It can be manufactured by That is,
For example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or molecular weight modifier, by the reaction of a dihydric phenol and a carbonate precursor such as phosgene, or in the presence or absence of a solvent, divalent It can be produced by a transesterification reaction of phenol and a carbonate precursor such as a carbonate compound.

As the dihydric phenol represented by the general formula (III), various ones can be mentioned. In particular,
2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A] is preferable. Bisphenol A
Examples of dihydric phenols other than bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane and other bis (4- Hydroxyphenyl) alkane, 1,1-bis (4-hydroxyphenyl) cyclohexane; bis (4-hydroxyphenyl) cycloalkane such as 1,1-bis (4-hydroxyphenyl) cyclodecane, 4,4′-dihydroxydiphenyl, Bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxy) Phenyl) ketone and the like can be mentioned. In addition to these, examples of the dihydric phenol include hydroquinone. Each of these divalent phenols may be used alone,
You may use it in mixture of 2 or more types.

Examples of the carbonic acid ester include diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate and diethyl carbonate.

In the present invention, when a linear polycarbonate resin is produced by reacting the above dihydric phenol with a carbonate precursor, an average carbon of an alkyl group is used as a terminal terminating agent (also referred to as a molecular weight modifier). Number is 8-17
Of mono-alkylphenol and p-tert-butylphenol (PTBP) are used. When a monoalkylphenol in which the average carbon number of the alkyl group is 8 to 17 is used, the average carbon number of the terminal alkyl group is 8 to 17
It is possible to obtain a linear polycarbonate resin having When PTBP is used, a linear polycarbonate resin having PTBP at the end can be obtained.
Furthermore, when a predetermined amount of a mixture of a monoalkylphenol having an alkyl group having an average carbon number of 8 to 17 and PTBP is used as a terminal terminator, the polycarbonate resin composition of the present invention can be produced simultaneously with the production of a linear polycarbonate resin. You can get things. Here, when the average carbon number of the alkyl group is less than 8, the improvement of fluidity is insufficient,
When it exceeds 17, the reactivity becomes poor and the loss of monoalkylphenol increases. More preferably, it has an average carbon number of 10 to 17, and even more preferably 12 to 1.
It has an average carbon number of 6. The average carbon number of the alkyl group is the sum of [the product of (the carbon number of the alkyl group) and (the mole fraction thereof)]. The above monoalkylphenols may be used alone or in combination of two or more. When two or more kinds are used in combination, the carbon number of the alkyl group is represented by the average carbon number.

Further, the above-mentioned monoalkylphenol includes isomers, ortho-form, meta-form and para-form, but any of them may be used. The alkyl group may be linear or branched. The linear polycarbonate of the present invention has a viscosity average molecular weight of 15, from the viewpoint of mechanical strength and moldability.
It must be in the range of 000 to 29,000. Preferably 17,000-27,000, more preferably 1700
It is in the range of 0 to 25,000. The viscosity average molecular weight (Mv) was measured by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, and determining the intrinsic viscosity [η] from this, [η] = 1.23 × 10 A value calculated by the formula of ^-5 Mv ^0.83 .

The unreacted monoalkylphenol of the linear polycarbonate of the present invention needs to be 300 ppm or less. The method for reducing the concentration to 300 ppm or less is not particularly limited. For example, in the solution method, precipitation of the polycarbonate generated in the poor solvent may be filtered and separated. If it exceeds 300 ppm, deposits are seen on the mold for injection molding, and the appearance of the molded product is not good, which is not preferable.

The linear polycarbonate of the present invention may optionally contain various additives such as an antioxidant, an ultraviolet absorber, a lightness improver, as long as the object of the present invention is not impaired.
A lubricant (release agent), a flame retardant, an anti-drip agent and other inorganic fillers may be appropriately contained. A composition can be prepared by mixing various additives into the polycarbonate of the present invention and kneading. As the compounding and kneading method, the method applied to a usual resin composition can be applied as it is, and a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single-screw or two or more multi-screw extruder, a co-kneader and the like can be used. The method used is preferred. The kneading temperature is not particularly limited, but usually 240
It is preferably selected from the range of to 340 ° C.

The resin composition thus obtained can be molded by a usual molding method such as injection molding or compression molding to obtain a molded article.

[0023]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Production Example [Synthesis of Monoalkylphenol (AP16)] In a 260 liter reaction tank equipped with a stirrer, 41.7 kg of 1-hexadecene, 70 kg of phenol, and galeonite # 136 as a catalyst [manufactured by Mizusawa Scientific Industrial Co., Ltd.] 7k
g was charged, and the reaction was carried out at 145 ° C. in a nitrogen stream for 80 minutes with stirring. After completion of the reaction, the catalyst was filtered off, and then the residue was separated from heavy components such as phenol and dialkylphenol by vacuum distillation to purify monoalkylphenol (AP16). As a result of analyzing the purified AP16 by gas chromatography, it was confirmed that
It contained 0 ppm, and no dialkylphenol peak was detected.

Example 1 1. Production of Polycarbonate Synthesis of Polycarbonate Oligomer Bisphenol A was dissolved in a 5.6% by mass aqueous sodium hydroxide solution so that the concentration of bisphenol A was 13.5% by mass to prepare an aqueous sodium hydroxide solution of bisphenol A. Phosgene was continuously supplied to a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 4.0 kg / hr at a flow rate of 40 liter / hr of sodium hydroxide aqueous solution of bisphenol A and 15 liter / hr of methylene chloride. The tubular reactor had a jacket, and cooling water was passed through the jacket to keep the temperature of the reaction solution at 40 ° C. or lower. The reaction liquid discharged from the tubular reactor was continuously introduced into a tank-type reactor with a baffle having an internal volume of 40 liters equipped with a retreating blade, and further 2.8 liters of a sodium hydroxide aqueous solution of bisphenol A was added thereto. hr, 25 mass% sodium hydroxide aqueous solution 0.07 liter / hr, water 17 liter / hr and 1 mass% triethylamine aqueous solution 0.64
Liter / hr, p-dodecylphenol (PDDP,
The reaction was carried out by supplying 2.15 liters / hr of a 7.0 mass% methylene chloride solution (produced by Yuka Schenectady). The reaction liquid overflowing from the tank reactor was continuously withdrawn and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected. The polycarbonate oligomer thus obtained had a concentration of 323 g / liter and a chloroformate group concentration of 0.69 mol / liter.

Synthesis of Polycarbonate In a 50 liter tank reactor equipped with baffles, two paddle type stirring blades and a cooling jacket, the above oligomer solution 10 was added.
Liter, 6.15 liters of methylene chloride, 88 g of PDDP as a terminal stopper, and 3.84 ml of triethylamine as a catalyst were charged, and 1720 g of a 6.4 mass% sodium hydroxide aqueous solution in which 226 mg of sodium dithionite was dissolved. Is added under stirring and 20
Reaction was performed for a minute. In this reaction step, the reaction temperature was controlled by cooling so as not to exceed 20 ° C.
Then, an aqueous sodium hydroxide solution of bisphenol A (331 g of NaOH, 1.32 of sodium dithionite).
bisphenol A (660 g dissolved in an aqueous solution in which 4. g of water was dissolved in 4.84 liters), and 300 r
The polymerization reaction was carried out for 40 minutes while stirring at pm.

To dilute the washing step, 10 liters of methylene chloride was added, and the mixture was left to stir for 20 minutes to separate it into an organic phase containing polycarbonate and an aqueous phase containing excess bisphenol A and sodium hydroxide, and the organic phase was reacted. It was extracted from the lower part of the vessel and isolated. A methylene chloride solution of the polycarbonate thus obtained was sequentially added to the solution in an amount of 0.03% by volume of 15%.
Washed with a mol / l sodium hydroxide aqueous solution, 0.2 mol / l hydrochloric acid, and then washed twice with pure water,
It was confirmed that the electric conductivity in the aqueous phase after washing was 0.01 μS / m or less.

Methylene chloride solution of polycarbonate obtained by washing in the flaking step is concentrated and pulverized, and the obtained flakes are reduced to 100 ° C. under reduced pressure.
Dried in. 2. Production of Polycarbonate Resin Composition PDDP-terminated polycarbonate resin and PTBP-terminated polycarbonate resin (FN1700) thus obtained
A, manufactured by Idemitsu Petrochemical Co., Ltd.) was blended at a ratio of 70/30 (mass ratio) and Tris (2,4) as a stabilizer.
-Di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Co .: lrgafos168) was added to 0.1 wt.
Mass% was blended, supplied to a vent type twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.), melt-kneaded at 280 ° C., extruded in a strand shape and then cut to obtain pellets of a polycarbonate resin composition. . Next, the obtained pellets are dried at 120 ° C. for 12 hours, and then the molding temperature is set to 270.
Various test pieces were obtained by injection molding at ℃ and mold temperature of 80 ℃. The evaluation results are shown in Table 1-1.

Example 2 of the first example. In the synthesis of polycarbonate, P
The DDP was changed to 76 g to obtain a PDDP-terminated polycarbonate resin. This PDDP terminal polycarbonate resin and PTBP terminal polycarbonate resin (FN1700
A, manufactured by Idemitsu Petrochemical Co., Ltd.) and PTBP-terminated polycarbonate resin (FN1900A, manufactured by Idemitsu Petrochemical Co., Ltd.)
Various test pieces were prepared from the pellets of the polycarbonate resin composition by blending at a ratio of 0/15/15 (mass ratio) in the same manner as in Example 1. The evaluation results are shown in Table 1-1.

Example 3 1. of Example 1. In the synthesis of polycarbonate, 26.5 g of PTBP and PDDP3 as end-stopping agents
After producing a linear polycarbonate resin in the same manner as in Example 1 except that 0.9 g was used, various test pieces were prepared from pellets of the polycarbonate resin composition. The evaluation results are shown in Table 1-1.

Example 4 Example 1 of 1. In the synthesis of polycarbonate, after the linear polycarbonate resin was produced in the same manner as in Example 1 except that 24.4 g of PTBP and 22.0 g of PDDP were used as the terminal terminator, various types were prepared from pellets of the polycarbonate resin composition. A test piece was prepared. The evaluation results are shown in Table 1-2.

Embodiment 5 1. of Embodiment 1. In the synthesis of the polycarbonate oligomer, the 8.5 mass% methylene chloride solution of AP16 was used in place of the 7.0 mass% methylene chloride solution of PDDP, and in the synthesis of the polycarbonate, 109.4 g of AP16 was used as a terminal stopper. A linear polycarbonate resin was produced in the same manner as in Example 1 except for the above. The thus obtained AP16-terminated polycarbonate resin and PTBP-terminated polycarbonate resin (FN1
700, manufactured by Idemitsu Petrochemical Co., Ltd.) was blended at a ratio of 50/50 to prepare a polycarbonate resin composition in the same manner as in Example 1, and various test pieces were prepared from the pellets. The evaluation results are shown in Table 1-2.

Example 6 Example 1 of Example 1. In the synthesis of the polycarbonate oligomer, the 8.5 mass% methylene chloride solution of AP16 was used in place of the 7.0 mass% methylene chloride solution of PDDP, and 44.3 g of PTBP was used as the terminal stopper in the synthesis of the polycarbonate. Example 1
After producing a linear polycarbonate resin in the same manner as above, various test pieces were prepared from pellets of the polycarbonate resin composition. The evaluation results are shown in Table 1-2.

Comparative Example 1 1. A resin composition was prepared in the same manner as in Example 1 using only the PDDP-terminated polycarbonate resin obtained in the flaking step, and various test pieces were prepared from pellets of the polycarbonate resin composition. The evaluation results are shown in Table 2-
Shown in 1.

Comparative Example 2 Polycarbonate manufactured by Idemitsu Petrochemical Co., Ltd.
Base, TAFRON FN1700A), and Example 1
A resin composition was prepared in the same manner as above, and various test pieces were prepared from pellets of the polycarbonate resin composition. The evaluation results are shown in Table 2-1.

Comparative Example 3 Example 1 of 1. A 8.5 mass% methylene chloride solution of AP16 was used in place of the 7.0 mass% methylene chloride solution of PDDP in the synthesis of the polycarbonate oligomer, and 109.4 g of AP16 was used as a terminal stopper in the synthesis of the polycarbonate. The resin composition was prepared in the same manner as in Example 1 using only the AP16-terminated polycarbonate resin obtained through the washing step and the flake step, and various test pieces were prepared from the pellets of the polycarbonate resin composition. The evaluation results are shown in Table 2-1.

Comparative Example 4 Example 1 of 1. PDDP-terminated polycarbonate resin obtained in the flaking process and polycarbonate manufactured by Idemitsu Petrochemical Co., Ltd. (PTBP group at the terminal, Tafflon FN1700
A) was blended at a ratio of 10/90 (mass ratio), and various test pieces were prepared from the pellets of the polycarbonate resin composition in the same manner as in Example 1. Table 2-2 shows the evaluation results.
Shown in.

Comparative Example 5 Example 1-2. PDDP-terminated polycarbonate resin obtained in the flaking process and polycarbonate manufactured by Idemitsu Petrochemical Co., Ltd. (PTBP group at the terminal, Tafflon FN1700
A) was blended at a ratio of 90/10 (mass ratio), and various test pieces were prepared from the pellets of the polycarbonate resin composition in the same manner as in Example 1. Table 2-2 shows the evaluation results.
Shown in.

The analysis of the above monoalkylphenol was carried out as follows. [Gas chromatographic analysis of monoalkylphenol (AP16)] Sample preparation: 0.1 g of AP16 was added to 50 ml of chloroform.
Dissolved in. Column: J & W SCIENTIFIC, HP-1
(15 m × 0.53 mmφ × 0.15 μm) Temperature pattern: 50 ° C./0 minute hold → 5 ° C./minute temperature rise → 40
Hold at 0 ° C / 20 minutes Carrier gas: Helium (21 kPa) Injection port: Splitless (200 ° C) Detector: 350 ° C Injection volume 1.0 μL

The above linear polycarbonate resin composition was evaluated as follows. (Evaluation of Polycarbonate Resin Composition) 1. Chemical resistance (critical strain) It was measured according to the chemical resistance evaluation method (critical strain by 1/4 ellipse). That is, test pieces (molding temperature 280 ° C., mold temperature 80 ° C., test piece size: 127 × 12.7 × 3 m)
m) is fixed to the 1/4 ellipsoidal surface of the jig shown in FIG. 1 (perspective view), and the test piece is covered with gauze impregnated with 1-methoxypropanol (Hiroshima Wako Pure Chemical Industries, Ltd.) to give 10 Hold for minutes. Then, the minimum length (X) at which a crack is generated is read, and the limit strain Y is calculated by the following equation (1).
(%) Was calculated. Critical strain (%) = (b / 2a ² ) [1- [1 / a ² − (b ²
/ A ⁴ )] X ² ] ^-3 / ² · t (t: thickness of test piece) 2. Fluidity (SFL) Injection pressure 80 kg / cm ² (7.84 MPa), molding temperature 2
The measurement was performed under the conditions of 80 ° C., mold temperature 80 ° C., width 10 mm, and wall thickness 2 mm. 3. Optical property: Yellow index Measured by a testing machine manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7103. As a test piece, 80 x 80 m
A square plate having a thickness of m and a thickness of 3 mm was used. According to Haze JIS K7105, parallel light transmittance was measured by a testing machine manufactured by Nippon Denshoku Industries Co., Ltd. As the test piece, a square plate having a wall thickness of 3.2 mm and 25 × 35 mm was used. 4. Izod impact strength According to ASTM D256, 23 ° C, 0 ° C and-
It was measured at 23 ° C. The test piece has a wall thickness of 3.1.
The thing of 8 mm was used.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

According to the present invention, it is possible to obtain a polycarbonate resin composition which is transparent, has a high fluidity, and has an excellent balance between fluidity and impact resistance. Further, the polycarbonate resin composition of the present invention is suitable as an optical information recording medium, a glazing material for the purpose of daylighting, a hard coat base material and the like.

[Brief description of drawings]

FIG. 1 is a perspective view of a test piece attachment jig for evaluating the chemical resistance (critical strain) of a linear polycarbonate resin of the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 CG01W CG01X GL00 GM00                       GQ00                 4J029 AA09 AB02 AE01 BB09 BB12                       BB13 BD09 BF03 BH02 DB09                       DB10 DB11 HA01 HC03 HC04                       HC05

Claims (2)

[Claims] 1. A monoalkylphenol having a terminal end,
A polycarbonate resin composition comprising a linear polycarbonate resin having an alkyl group having an average carbon number of 8 to 17 and a linear polycarbonate resin having a terminal of p-tert-butylphenol. 2. A monoalkylphenol having a terminal end,
A linear polycarbonate resin having an alkyl group with an average carbon number of 8 to 17 of 20 to 80 mass% and a terminal of p-ter
A polycarbonate resin composition comprising 80 to 20% by mass of a linear polycarbonate resin which is t-butylphenol.