Polycarbonate resin, and production method and film thereof

Abstract

To provide a polycarbonate resin having an excellent hue and high heat stability, and a production method and a film thereof. The polycarbonate resin has a carbonate constituent unit represented by the following formula (A), wherein the resin contains a terminal group represented by the following formula (1) or (2) and 0.1 to 500 ppm of an aromatic monohydroxy compound. ##STR00001## (In the formula (1), R.sub.1 is an alkyl group having 6 to 15 carbon atoms which may be substituted.) ##STR00002## (In the formula (2), R.sub.2 and R.sub.3 are each independently an alkylene group having 1 to 12 carbon atoms which may be substituted. R.sub.4 is a hydrogen atom or alkyl group having 1 to 12 carbon atoms which may be substituted. n is an integer of 1 to 20.)

Claims

1. A polycarbonate resin having a carbonate constituent unit represented by the following formula (A), wherein the polycarbonate resin contains a terminal group represented by the following formula (1) or (2), which is a residue of an alcohol compound having a boiling point at normal pressure of 190 to 300 C., and 0.1 to 500 ppm of an aromatic monohydroxy compound, ##STR00020## wherein R.sub.1 is an alkyl group having 6 to 15 carbon atoms which may be substituted, an alkoxy group having 6 to 15 carbon atoms which may be substituted, an aryl group having 6 to 14 carbon atoms which may be substituted, an alkenyl group having 6 to 15 carbon atoms which may be substituted, or an aralkyl group having 7 to 15 carbon atoms which may be substituted, ##STR00021## wherein R.sub.2 and R.sub.3 are each independently an alkylene group having 1 to 12 carbon atoms which may be substituted, an arylene group having 6 to 14 carbon atoms which may be substituted, an alkenylene group having 2 to 12 carbon atoms which may be substituted, an arylalkylene group having 7 to 15 carbon atoms which may be substituted, or an alkylarylene group having 7 to 15 carbon atoms which may be substituted, wherein R.sub.4 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted, an aryl group having 6 to 14 carbon atoms which may be substituted, an alkenyl group having 2 to 12 carbon atoms which may be substituted, or an aralkyl group having 7 to 15 carbon atoms which may be substituted, n is an integer of 1 to 20.).

2. The polycarbonate resin according to claim 1, wherein the content of the carbonate constituent unit represented by the formula (A) is 50 to 94 mol % based on the total of all carbonate constituent units.

3. The polycarbonate resin according to claim 1, further comprising a carbonate constituent unit represented by the following formula (B-1), ##STR00022## wherein W is an alkylene group having 2 to 30 carbon atoms, a cycloalkylene group having 6 to 30 carbon atoms or CH.sub.2ZCH.sub.2, wherein Z is a cycloalkylene group having 6 to 30 carbon atoms, wherein the molar ratio (A/B-1) of the unit (A) and the unit (B-1) is 60/40 to 90/10.

4. The polycarbonate resin according to claim 1, wherein the formula (A) represents a carbonate constituent unit derived from isosorbide.

5. The polycarbonate resin according to claim 1, wherein the content of the terminal group represented by the formula (1) or (2) is 10 to 90 mol % based on the total of all terminal groups.

6. The polycarbonate resin according to claim 1, wherein the specific viscosity of a 20 C. methylene chloride solution of the polycarbonate resin is 0.18 to 0.5.

7. A method of producing the polycarbonate resin of claim 1, comprising the step of reacting a dihydroxy compound containing isosorbide, a carbonic diester and an alcohol compound having a boiling point at normal pressure of 190 to 300 C. represented by the following formula (a) or (b), ##STR00023## wherein R.sub.1 is as defined in the above formula (1), ##STR00024## wherein R.sub.2, R.sub.3, R.sub.4 and n are as defined in the above formula (2).

8. The production method according to claim 7, wherein the alcohol compound represented by the formula (a) or (b) is reacted in an amount of 0.1 to 5 mol % based on the total of all dihydroxy compounds.

9. The production method according to claim 7, wherein the alcohol compound represented by the formula (a) or (b) has a boiling point at normal pressure of 230 to 300 C.

10. A film made of the polycarbonate resin of claim 1.

11. The film made of the polycarbonate resin of claim 1, wherein R.sub.1 is an alkyl group having 6 to 15 carbon atoms which may be substituted or an alkoxy group having 6 to 15 carbon atoms which may be substituted in the formula (1), R.sub.2 and R.sub.3 are each independently an alkylene group having 1 to 12 carbon atoms which may be substituted, R.sub.4 is a hydrogen atom or alkyl group having 1 to 12 carbon atoms which may be substituted, and n is an integer of 1 to 20 in the formula (2).

12. The film according to claim 11 which has a transmittance at 260 nm of not less than 30% and a transmittance at 280 nm of not less than 20%.

13. The film according to claim 11 which is a film for agricultural houses, dust-proof film or food packaging film.

Description

EXAMPLES

(1) The following examples are provided for the purpose of further illustrating the present invention but are in no way to be taken as limiting. Parts in the examples means parts by weight. Resins and evaluation methods used in the examples are as follows.

(2) 1. Polymer Terminal Ratio (NMR)

(3) Each of the recurring units was measured with the proton NMR of the JNM-AL400 of JEOL Ltd. to calculate the polymer terminal ratio (molar ratio).

(4) 2. Measurement of Specific Viscosity

(5) This was obtained from a solution prepared by dissolving 0.7 g of the polycarbonate copolymer in 100 ml of methylene chloride at 20 C. by using an Ostwald viscometer.
Specific viscosity(.sub.sp)=(tt.sub.0)/t.sub.0
[t.sub.0 is the number of seconds required for the dropping of methylene chloride, and t is the number of seconds required for the dropping of a sample solution]
3. Amount of Residual Phenol

(6) After 1.5 g of the polycarbonate copolymer was dissolved in 15 ml of methylene chloride, 135 ml of acetonitrile was added, stirred and concentrated with an evaporator, the resulting solution was filtered with a 0.2 m filter, and HPLC analysis was made on 10 l of this measurement solution at a column temperature of 30 C. and a detector wavelength of 277 nm by using the Develosil ODS-7 column of Nomura Chemical Co., Ltd., a mixed solution of 0.2% acetic acid water and acetonitrile as an elute acetonitrile and a gradient program.

(7) 4. Heat Stability Test

(8) After 5 g of the polycarbonate copolymer was put into a test tube and heated at 280 C. for 15 minutes in a nitrogen atmosphere, the specific viscosity of the polycarbonate copolymer was measured. means that there was a reduction of 5% or less from the initial specific viscosity, means that there was a reduction of more than 5% to less than 8%, and X means that there was a reduction of 8% or more.

(9) 5. Hue (YI)

(10) After the polycarbonate copolymer was dried at 100 C. for 6 hours, it was molded at a cylinder temperature of 240 C. and a mold temperature of 80 C. by means of an injection molding machine (JSWJ-75EIII of The Japan Steel Works, Ltd.) to obtain a molded test sample having a thickness of 2 mm. The YI value of the molded 2.0 mm-thick plate was calculated by the following equation based on ASTME1925 from X, Y and Z values obtained by measuring transmitted light with the Z-1001DP color difference meter of Nippon Denshoku Industries Co., Ltd. As the larger the YI value the stronger the yellow tinge of the molded plate becomes.
YI=[100(1.28X1.06Z)]/Y
6. Ultraviolet Transmittance

(11) The transmittances at 260 nm and 280 nm of a film having a thickness of 100 m were measured by using the U-3310 spectrophotometer of Hitachi, Ltd.

Example 1

(12) 432 parts of isosorbide (to be abbreviated as ISS hereinafter), 84 parts of 1,9-nonanediol (to be abbreviated as ND hereinafter), 9.5 parts of phenoxy ethanol, 750 parts of diphenyl carbonate (to be abbreviated as DPC hereinafter) and 0.0025 part of barium stearate as a catalyst were heated at 120 C. in a nitrogen atmosphere to be molten. Thereafter, the resulting solution was supplied into a reaction tank, the heat medium temperature of a capacitor was adjusted to 40 C., the internal temperature of the resin was adjusted to 170 C., and the decompression degree was adjusted to 13.4 kPa over 30 minutes.

(13) (Step A)

(14) Thereafter, the decompression degree was adjusted to 3.4 kPa over 20 minutes, and the resin temperature was adjusted to 170 C. and kept at that temperature for 10 minutes to carry out sampling. The obtained sample had a specific viscosity of 0.023.

(15) (Step B)

(16) After the decompression degree was further adjusted to 0.9 kPa over 30 minutes and the internal temperature of the resin was adjusted to 180 C. and kept at that temperature for 10 minutes, sampling was carried out. The obtained sample had a specific viscosity of 0.081.

(17) (Step C)

(18) After the decompression degree was further adjusted to 0.2 kPa, the resin temperature was raised from 180 C. to 225 C. over 30 minutes, and specified viscosity was attained, the sample was discharged under nitrogen increased pressure from the bottom of the reaction tank and cut with a pelletizer while cooled in a water tank to obtain a pellet. When the specific viscosity and the amount of the residual phenol of the pellet were measured, the specific viscosity was 0.375 and the amount of the residual phenol was 164 ppm.

(19) 1,000 parts of the obtained polycarbonate resin and 0.3 part of tris(2,4-di-tert-butylphenyl)phosphite were extruded into a strand by using a vented double-screw extruder having a diameter of 30 mm, and the strand was cooled in 40 C. hot water and cut to obtain a resin pellet of the polycarbonate resin composition. Thereafter, the pellet was dried at 110 C. for 3 hours with a hot air circulation drier and molded at a cylinder temperature of 230 C. and a mold temperature of 80 C. by using an injection molding machine (JSWJ-75EIII of The Japan Steel Works, Ltd.) to obtain a 2 mm-thick plate test sample. The evaluation results are shown in Table 1.

Example 2

(20) The same operation and the same evaluations as in Example 1 were made except that the amount of phenoxy ethanol was changed to 14.2 parts. The results are shown in Table 1. The specific viscosity of the sample of the step A was 0.021, the specific viscosity of the sample of the step B was 0.082, the specific viscosity of the pellet obtained after the step C was 0.317, and the amount of the residual phenol was 121 ppm.

Example 3

(21) The same operation and the same evaluations as in Example 1 were made except that the amount of phenoxy ethanol was changed to 2.4 parts. The results are shown in Table 1. The specific viscosity of the sample of the step A was 0.025, the specific viscosity of the sample of the step B was 0.087, the specific viscosity of the pellet obtained after the step C was 0.367, and the amount of the residual phenol was 463 ppm.

Example 4

(22) The same operation and the same evaluations as in Example 1 were made except that the amount of phenoxy ethanol was changed to 9.5 parts and the amount of tridecanol was changed to 13.8 parts. The results are shown in Table 1. The specific viscosity of the sample of the step A was 0.026, the specific viscosity of the sample of the step B was 0.086, the specific viscosity of the pellet obtained after the step C was 0.358, and the amount of the residual phenol was 231 ppm.

Example 5

(23) The same operation and the same evaluations as in Example 1 were made except that the amount of phenoxy ethanol was changed to 9.5 parts and the amount of decanol was changed to 10.8 parts. The results are shown in Table 1. The specific viscosity of the sample of the step A was 0.019, the specific viscosity of the sample of the step B was 0.078, the specific viscosity of the pellet obtained after the step C was 0.387, and the amount of the residual phenol was 98 ppm.

Example 6

(24) The same operation and the same evaluations as in Example 1 were made except that 356 parts of ISS, 151 parts of 1,4-cyclohexane dimethanol (to be abbreviated as CHDM hereinafter), 9.5 parts of phenoxy ethanol and 750 parts of DPC were used as raw materials. The results are shown in Table 1. The specific viscosity of the sample of the step A was 0.021, the specific viscosity of the sample of the step B was 0.083, the specific viscosity of the pellet obtained after the step C was 0.352, and the amount of the residual phenol was 153 ppm.

Example 7

(25) The same operation and the same evaluations as in Example 1 were made except that 254 parts of ISS, 251 parts of CHDM, 9.5 parts of phenoxy ethanol and 750 parts of DPC were used as raw materials. The results are shown in Table 1. The specific viscosity of the sample of the step A was 0.029, the specific viscosity of the sample of the step B was 0.091, the specific viscosity of the pellet obtained after the step C was 0.423, and the amount of the residual phenol was 168 ppm.

Comparative Example 1

(26) The same operation and the same evaluations as in Example 1 were made except that phenoxy ethanol was not used. The results are shown in Table 1. The specific viscosity of the sample of the step A was 0.024, the specific viscosity of the sample of the step B was 0.092, the specific viscosity of the pellet obtained after the step C was 0.359, and the amount of the residual phenol was 2,983 ppm.

Comparative Example 2

(27) The same operation and the same evaluations as in Example 1 were made except that 0.96 part of phenoxy ethanol was used. The results are shown in Table 1. The specific viscosity of the sample of the step A was 0.021, the specific viscosity of the sample of the step B was 0.089, the specific viscosity of the pellet obtained after the step C was 0.360, and the amount of the residual phenol was 2,550 ppm.

Comparative Example 3

(28) The same operation and the same evaluations as in Example 1 were made except that 7.0 parts of hexanol was used in place of 9.5 parts of phenoxy ethanol. The results are shown in Table 1. The specific viscosity of the sample of the step A was 0.023, the specific viscosity of the sample of the step B was 0.093, the specific viscosity of the pellet obtained after the step C was 0.385, and the amount of the residual phenol was 2,855 ppm.

Comparative Example 4

(29) The same operation and the same evaluations as in Example 1 were made except that 18.5 parts of stearyl alcohol was used in place of 9.5 parts of phenoxy ethanol. The results are shown in Table 1. The specific viscosity of the sample of the step A was 0.025, the specific viscosity of the sample of the step B was 0.087, the specific viscosity of the pellet obtained after the step C was 0.276, and the amount of the residual phenol was 2,582 ppm.

Comparative Example 5

(30) The same operation and the same evaluations as in Example 1 were made except that 21.2 parts of pentadecyl phenol was used in place of 9.5 parts of phenoxy ethanol. The results are shown in Table 1. The specific viscosity of the sample of the step A was 0.022, the specific viscosity of the sample of the step B was 0.074, the specific viscosity of the pellet obtained after the step C was 0.246, and the amount of the residual phenol was 2,897 ppm.

(31) TABLE-US-00001 TABLE 1 boiling point amount of Constituent monomers (molar ratio) type of alcohol of alcohol alcohol Recurring unit (A) Recurring unit (B) C. mol % Ex. 1 ISS 85 ND 15 phenoxy ethanol 240 2 Ex. 2 ISS 85 ND 15 phenoxy ethanol 240 3 Ex. 3 ISS 85 ND 15 phenoxy ethanol 240 0.5 Ex. 4 ISS 85 ND 15 Tridcanol 255 2 Ex. 5 ISS 85 ND 15 Decanol 230 4 Ex. 6 ISS 70 CHDM 30 phenoxy ethanol 240 2 Ex. 7 ISS 50 CHDM 50 phenoxy ethanol 240 2 C. Ex. 1 ISS 85 ND 15 0 C. Ex. 2 ISS 85 ND 15 phenoxy ethanol 240 0.2 C. Ex. 3 ISS 85 ND 15 Hexanol 157 2 C. Ex. 4 ISS 85 ND 15 Stearyl alcohol 351 2 C. Ex. 5 ISS 85 ND 15 Pentadecyl phenol >380 2 terminal terminal terminal residual heat Specific alcohol phenyl group OH group PhOH stability viscosity % % % ppm test YI Ex. 1 0.375 24 37 39 164 1.9 Ex. 2 0.317 32 28 40 121 1.8 Ex. 3 0.367 8 56 36 463 2.1 Ex. 4 0.358 28 39 33 231 1.9 Ex. 5 0.387 65 17 18 98 1.8 Ex. 6 0.352 26 35 39 153 1.8 Ex. 7 0.423 29 41 30 168 1.8 C. Ex. 1 0.359 55 45 2983 X 1.7 C. Ex. 2 0.360 3 54 43 2550 X 2.7 C. Ex. 3 0.385 4 56 40 2855 X 2.8 C. Ex. 4 0.276 73 16 11 2582 X 2.6 C. Ex. 5 0.246 69 14 17 2897 X 2.8 Ex.: Example C. Ex.: Comparative Example

Example 8

(32) 432 parts of isosorbide (ISS), 84 parts of 1,9-nonanediol (to be abbreviated as ND hereinafter), 20.9 parts of tridecanol, 750 parts of diphenyl carbonate (to be abbreviated as DPC hereinafter) and 0.0025 part of barium stearate as a catalyst were heated at 120 C. in a nitrogen atmosphere to be molten. Thereafter, the resulting solution was supplied into a reaction tank, the heat medium temperature of a capacitor was adjusted to 40 C., the internal temperature of the resin was adjusted to 170 C. and the decompression degree was adjusted to 13.4 kPa over 30 minutes.

(33) (Step A)

(34) Thereafter, the decompression degree was adjusted to 3.4 kPa over 20 minutes, and the resin temperature was adjusted to 170 C. and kept at that temperature for 10 minutes to carry out sampling. The obtained sample had a specific viscosity of 0.021.

(35) (Step B)

(36) The decompression degree was further adjusted to 0.9 kPa over 30 minutes, and the resin temperature was adjusted to 180 C. and kept at that temperature for 10 minutes to carry out sampling. The obtained sample had a specific viscosity of 0.080.

(37) (Step C)

(38) After the decompression degree was further adjusted to 0.2 kPa, the resin temperature was raised from 180 C. to 225 C. over 30 minutes, and specified viscosity was attained, the sample was discharged under nitrogen increased pressure from the bottom of the reaction tank and cut with a pelletizer while cooled in a water tank to obtain a pellet. When the specific viscosity and the amount of the residual phenol of the pellet were measured, the specific viscosity was 0.358 and the amount of the residual phenol was 120 ppm.

(39) (Film Formation)

(40) Then, a vacuum hopper whose vacuum degree was adjusted to 1 kPa or less and a T die having a width of 650 mm were set in a 40 mm-diameter single-screw extruder, and the obtained polycarbonate resin pellet was formed at 240 C. to obtain a transparent extrusion film having a thickness of 100 m. The transmittance of the obtained film was measured.

Example 9

(41) The same operation and the same evaluations as in Example 8 were made except that 22.1 parts of decanol was used in place of 20.9 parts of tridecanol. The specific viscosity of the sample of the step A was 0.022, the specific viscosity of the sample of the step B was 0.084, the specific viscosity of the pellet obtained after the step C was 0.387, and the amount of the residual phenol was 132 ppm. The results are shown in Table 2.

Example 10

(42) The same operation and the same evaluations as in Example 8 were made except that 27.6 parts of decanol was used in place of 20.9 parts of tridecanol. The specific viscosity of the sample of the step A was 0.018, the specific viscosity of the sample of the step B was 0.077, the specific viscosity of the pellet obtained after the step C was 0.387, and the amount of the residual phenol was 86 ppm. The results are shown in Table 2.

Example 11

(43) The same operation and the same evaluations as in Example 8 were made except that 356 parts of ISS, 151 parts of 1,4-cyclohexane dimethanol (to be abbreviated as CHDM hereinafter), 22.1 parts of decanol and 750 parts of DPC were used as raw materials. The specific viscosity of the sample of the step A was 0.023, the specific viscosity of the sample of the step B was 0.082, the specific viscosity of the pellet obtained after the step C was 0.352, and the amount of the residual phenol was 125 ppm. The results are shown in Table 2.

Example 12

(44) The same operation and the same evaluations as in Example 8 were made except that 254 parts of ISS, 251 parts of 1,4-cyclohexane dimethanol (to be abbreviated as CHDM hereinafter), 22.1 parts of decanol and 750 parts of DPC were used as raw materials. The specific viscosity of the sample of the step A was 0.025, the specific viscosity of the sample of the step B was 0.092, the specific viscosity of the pellet obtained after the step C was 0.423, and the amount of the residual phenol was 106 ppm. The results are shown in Table 2.

Example 13

(45) The same operation and the same evaluations as in Example 8 were made except that 254 parts of ISS, 251 parts of 1,4-cyclohexane dimethanol (to be abbreviated as CHDM hereinafter), 11.1 parts of decanol and 750 parts of DPC were used as raw materials. The specific viscosity of the sample of the step A was 0.027, the specific viscosity of the sample of the step B was 0.095, the specific viscosity of the pellet obtained after the step C was 0.432, and the amount of the residual phenol was 248 ppm. The results are shown in Table 2.

Comparative Example 6

(46) The same operation and the same evaluations as in Example 8 were made except that tridecanol was not used. The specific viscosity of the sample of the step A was 0.024, the specific viscosity of the sample of the step B was 0.092, the specific viscosity of the pellet obtained after the step C was 0.359, and the amount of the residual phenol was 2,983 ppm. The results are shown in Table 2.

Comparative Example 7

(47) The same operation as in Example 8 was carried out after a low-molecular weight material was devolatilized from a vent by the water-pouring devolatilization of the polycarbonate obtained in Comparative Example 6 with a 30 mm-diameter double-screw extruder. The results are shown in Table 2. The specific viscosity of the sample of the step A was 0.024, the specific viscosity of the sample of the step B was 0.092, the specific viscosity of the pellet obtained after the step C was 0.354, and the amount of the residual phenol was 581 ppm.

Comparative Example 8

(48) The same operation and the same evaluations as in Example 8 were made except that 7.0 parts of hexanol was used in place of 20.9 parts of tridecanol. The results are shown in Table 2. The specific viscosity of the sample of the step A was 0.023, the specific viscosity of the sample of the step B was 0.093, the specific viscosity of the pellet obtained after the step C was 0.385, and the amount of the residual phenol was 2,855 ppm.

Comparative Example 9

(49) The same operation and the same evaluations as in Example 8 were made except that 18.5 parts of stearyl alcohol was used in place of 20.9 parts of tridecanol. The results are shown in Table 2. The specific viscosity of the sample of the step A was 0.025, the specific viscosity of the sample of the step B was 0.087, the specific viscosity of the pellet obtained after the step C was 0.276, and the amount of the residual phenol was 2,582 ppm.

Comparative Example 10

(50) The same operation and the same evaluations as in Example 8 were made except that 21.1 parts of pentadecyl phenol was used in place of 20.9 parts of tridecanol. The results are shown in Table 2. The specific viscosity of the sample of the step A was 0.022, the specific viscosity of the sample of the step B was 0.074, the specific viscosity of the pellet obtained after the step C was 0.246, and the amount of the residual phenol was 2,897 ppm.

(51) TABLE-US-00002 TABLE 2 boiling point amount of Constituent monomers (molar ratio) type of alcohol of alcohol alcohol Recurring unit (A) Recurring unit (B) C. mol % Ex. 8 ISS 85 ND 15 Tridcanol 255 3 Ex. 9 ISS 85 ND 15 Decanol 230 4 Ex. 10 ISS 85 ND 15 Decanol 230 5 Ex. 11 ISS 70 CHDM 30 Decanol 230 4 Ex. 12 ISS 50 CHDM 50 Decanol 230 4 Ex. 13 ISS 50 CHDM 50 Decanol 230 2 C. Ex. 6 ISS 85 ND 15 0 C. Ex. 7 ISS 85 ND 15 0 C. Ex. 8 ISS 85 ND 15 Hexanol 157 2 C. Ex. 9 ISS 85 ND 15 Stearyl alcohol 351 2 C. Ex. 10 ISS 85 ND 15 Pentadecyl phenol >380 2 terminal terminal terminal residual transmittance Specific alcohol phenyl group OH group PhOH 260 nm 280 nm viscosity % % % ppm % % Ex. 8 0.358 69 12 19 120 74 75 Ex. 9 0.387 65 16 19 132 73 74 Ex. 10 0.387 76 9 15 86 76 78 Ex. 11 0.352 68 11 21 125 74 76 Ex. 12 0.423 71 12 17 106 73 74 Ex. 13 0.432 52 25 23 248 56 58 C. Ex. 6 0.359 55 45 2983 10 8 C. Ex. 7 0.354 46 54 581 12 10 C. Ex. 8 0.385 4 56 40 2855 11 9 C. Ex. 9 0.276 73 16 11 2582 13 11 C. Ex. 10 0.246 69 14 17 2897 9 7 Ex.: Example C. Ex.: Comparative Example

INDUSTRIAL FEASIBILITY

(52) Since the polycarbonate resin of the present invention is excellent in hue and heat stability, it can be used for various purposes such as optical, disk, display, automobile, electric and electronic and decoration purposes. The film of the present invention has excellent transmittance at a specific wavelength (ultraviolet light) and can be used as a film for agricultural houses, dust-proof film, food packaging film or lighting cover (especially cover for ultraviolet lamps).