JPH07173278A - Modified aromatic polycarbonate resin - Google Patents

Abstract

PURPOSE:To obtain a modified aromatic polycarbonate resin improved in moldability and tracking resistance while retaining the transparency and mechanical properties by introducing specified structural units into the principal chain of an aromatic polycarbonate resin. CONSTITUTION:Structural units represented by formula I (wherein R<1> is an aliphatic group which may contain a 1-10C ether group; R<2> is a 1-10C aliphatic group or halogen; m is 0 to 4; n is 1 to 100; and p is 0 to 4) are incorporated into an aromatic polycarbonate resin made from a dihydric phenol and a carbonate precusor so as to provide a content of the structural units of 1-99 % based on the total number of structural units of the modified aromatic polycarbonate resin. To introduce the units of formula I into the principal chain of an aromatic polycarbonate resin, a compound of formula II is used together with the dihydric phenol and the carbonate precursor. The compound of formula II is obtained by mixing a substituted hydroxyaralkyl alcohol with lactone and heating the mixture.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a modified aromatic polycarbonate resin. More specifically, it relates to a modified aromatic polycarbonate resin having improved melt flowability and tracking resistance.

[0002]

2. Description of the Related Art Conventionally, a typical aromatic polycarbonate resin is one obtained by reacting 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) with a carbonate precursor such as phosgene or diphenyl carbonate. Are known. Such aromatic polycarbonate resins have excellent properties such as transparency, heat resistance and good dimensional accuracy, and are therefore used in many fields.
Further, in recent years, it has also been widely used as a substrate for information recording media in the field of optical disks and the like. However, in recent years, in consideration of lightness, thinness and shortness, there has been a demand for a resin having a better melt fluidity and transferability and a shorter molding cycle. Further, in electrical applications, improvement in tracking resistance is also required. As a method for improving the melt fluidity of an aromatic polycarbonate resin, a method of lowering the average molecular weight as much as possible, a method of adding a plasticizer, a method of imparting a long chain aliphatic hydrocarbon substituent to a polymer terminal, a method of polymer blending Etc. have been devised. However, these methods tend to cause unfavorable problems such as deterioration of physical properties and loss of transparency.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic polycarbonate resin having improved properties such as moldability and tracking resistance while maintaining excellent transparency and mechanical properties. .

The inventor of the present invention intends to achieve the above object.
As a result of intensive studies on modification of aromatic polycarbonate resin, when a structural unit having a specific structure obtained by reacting hydroxyaralkyl alcohol and lactone is introduced into the main chain of aromatic polycarbonate resin, It has been found that the melt fluidity and tracking resistance can be improved while maintaining excellent transparency and mechanical properties. The present invention has been completed through further research based on this finding.

[0005]

The present invention provides an aromatic polycarbonate resin composed of a dihydric phenol and a carbonate precursor with the following general formula [1].

[0006]

[Chemical 2]

[In the formula, R ₁ is a divalent aliphatic group which may contain an ether group having 1 to 10 carbon atoms, R ₂ is a monovalent aliphatic group having 1 to 10 carbon atoms, or Halogen atom,
m is an integer of 0 to 4, n is an integer of 1 to 100, p is 0 to 4
Is an integer of 1 to 99 relative to the total number of modified aromatic polycarbonate resin structural units.
% Modified aromatic polycarbonate resin.

Examples of the dihydric phenol constituting the aromatic polycarbonate resin to be modified include hydroquinone, resorcin, 4,4'-dihydroxydiphenyl,
Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis ( 4-hydroxyphenyl) cyclohexane, 2,2-bis (3-phenyl-4)
-Hydroxyphenyl) propane, 2,2-bis (3-
Isopropyl-4-hydroxyphenyl) propane,
2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-)
Hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 4, 4'-dihydroxydiphenyl oxide, 9,9-bis (4-hydroxyphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,
Examples thereof include 3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane. Among them, bisphenol A, 1,1-bis (4-hydroxyphenyl) cyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, and 1,1-bis (4-hydroxyphenyl) -3 are large in that the improvement effect is large. , 3,5-Trimethylcyclohexane, 1,3-bis (4-hydroxyphenyl)-
5,7-Dimethyl adamantane is preferred. You may use these individually or in combination of 2 or more types. Also, a small amount of a trifunctional compound may be used as a branching agent, or a small amount of an aliphatic bifunctional compound may be used in combination.

Examples of the carbonate precursor include phosgene, phosgene dimer, phosgene trimer, and bischloroformate of the above dihydric phenols, and among them, phosgene is preferable. Further, for example, carbonic acid diesters such as diphenyl carbonate, dinaphthyl carbonate, ditolyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate can be mentioned, and among them, diphenyl carbonate is preferable.

To introduce the structural unit represented by the general formula [1] into the main chain of the aromatic polycarbonate resin, the following general formula [2]

[0011]

[Chemical 3]

A compound represented by the formula [wherein R ₁ , R ₂ , m, n and p are the same as those in the above general formula [1]] is used. As the divalent aliphatic group represented by R ₁ in the formula, an alkylene group having 1 to 10 carbon atoms is preferable, and an ether group may be contained. The monovalent aliphatic group represented by R ₂ is preferably an alkyl group having 1 to 10 carbon atoms. Such a compound is produced by reacting a substituted or unsubstituted hydroxyaralkyl alcohol and a lactone in an appropriate ratio and heating the mixture to react the alcoholic OH group with the lactone and the ring-opening reaction of the lactone. Can be arbitrarily controlled by adjusting the molar ratio of lactone to hydroxyaralkyl alcohol. If the repeating number of the lactone unit becomes too large, the reactivity of the terminal OH group decreases, so the repeating number of the lactone unit is preferably 1 to 100.

The amount of the compound represented by the general formula [2] used varies depending on the kind of the dihydric phenol used in the production of the aromatic polycarbonate resin, the intended use of the modified aromatic polycarbonate resin obtained, and the like, and is in an extremely wide range. It can be selected from the range of 1 to 99 mol% with respect to the total molar amount of the dihydric phenol used for the production of the aromatic polycarbonate resin and the compound represented by the above general formula [2]. If the amount is less than 1 mol%, it will be difficult to sufficiently improve the characteristics such as moldability and tracking resistance of the obtained aromatic polycarbonate resin. When the resulting modified aromatic polycarbonate resin is used alone, if the amount of the compound represented by the general formula [2] used increases, the original excellent properties of the aromatic polycarbonate resin will be impaired. ~ 50 mol% is suitable, 1-3
0 mol% is preferable. The resulting modified aromatic polycarbonate resin can be blended with an unmodified aromatic polycarbonate resin or another thermoplastic resin to improve properties such as moldability and tracking resistance. When the modified aromatic polycarbonate resin is used as a modifier in this way, the amount of the compound represented by the general formula [2] used is appropriately 30 to 99 mol%, preferably 50 to 99 mol%. 99
If it exceeds mol%, the compatibility with the unmodified aromatic polycarbonate resin will decrease.

Examples of the substituted or unsubstituted hydroxyaralkyl alcohol which gives the compound represented by the above general formula [2] include 2-hydroxybenzyl alcohol and 3-hydroxybenzyl alcohol.
Hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-bromo-5-hydroxybenzyl alcohol, 3-chloro-4-hydroxybenzyl alcohol, 3-hydroxy-α-methylbenzyl alcohol, 4-hydroxy-α-methylbenzyl alcohol,
2- (2-hydroxyphenyl) ethanol, 2- (4
-Hydroxyphenyl) ethanol, 2-methyl-4-
Hydroxyphenylbenzyl alcohol, 2-methyl-
6-hydroxyphenylbenzyl alcohol, 2-hydroxy-3-methylphenylbenzyl alcohol, 2-
Hydroxy-5-methylphenylbenzyl alcohol,
1- (4-hydroxyphenyl) propanol-2,3
-(2-hydroxyphenyl) propanol, 3- (3
-Hydroxyphenyl) propanol, 2-hydroxy-5-ethylbenzyl alcohol, 3-methyl-4-hydroxyphenyl-α-methylbenzyl alcohol, 4
-(2-Hydroxyphenyl) butanol-2,3-
(2-hydroxy-5-methylphenyl) propanol, 5- (2-hydroxyphenyl) pentanol, 4
-(2-Methyl-4-hydroxyphenyl) butanol-2,4- (3-methyl-4-hydroxyphenyl) butanol-2,3- (2-hydroxy-4-methylphenyl) butanol, 6- (4- Examples thereof include hydroxyphenyl) hexanol-2 and 4- (4-hydroxyphenyl) hexanol-3.

The lactone is a lactone having 5 to 21 carbon atoms, and a carbon atom forming the lactone ring may be substituted with a lower alkyl group. Examples of such lactones include δ-valerolactone, 7-hydroxyheptanoic acid lactone, 8-hydroxyoctanoic acid lactone, 13-hydroxytridecanoic acid lactone, 15-hydroxypentadecanoic acid lactone, 17-hydroxyheptadecanoic acid lactone, and monomethyl-δ. -Valerolactone, monoethyl-
Examples include δ-valerolactone, ε-caprolactone, monomethyl-ε-caprolactone, monoethyl-ε-caprolactone and the like. In particular, δ-valerolactone and ε-caprolactone are preferable.

The modified aromatic polycarbonate resin of the present invention is produced by a method used for producing an ordinary aromatic polycarbonate resin, for example, a method of reacting a dihydric phenol with a carbonate precursor such as phosgene or carbonic acid diester. . That is, it is produced by reacting a predetermined ratio of the compound of the general formula [2], the dihydric phenol and the carbonate precursor.

When phosgene, phosgene dimer, phosgene trimer, bischloroformate of the above dihydric phenols, etc. are used as the carbonate precursor, an amine catalyst such as pyridine and an acid are usually used in an anhydrous organic solvent. The reaction is carried out with a molecular weight regulator in the presence of a binder. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. As the molecular weight regulator, for example, monofunctional phenols such as phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol are preferably used. The reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

In the transesterification reaction using a carbonic acid diester as a carbonate precursor, a compound of the above-mentioned general formula [2] and a dihydric phenol in a predetermined ratio in an inert gas atmosphere are produced by stirring the carbonic acid diester while heating. It is carried out by distilling off the alcohol or phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 300 ° C. In the latter stage of the reaction, the system is depressurized to facilitate the distillation of the alcohol or phenol produced and complete the reaction. Further, a catalyst usually used in transesterification reaction can be used to accelerate the reaction.

The molecular weight of the modified aromatic polycarbonate resin thus obtained does not need to be limited,
Dissolve 0.7 g of polymer in 100 ml of methylene chloride to prepare 2
It is preferable that the specific viscosity of the solution measured at 0 ° C. is 0.165 or more. Those having a specific viscosity of less than 0.165 are fragile and impractical by themselves, but can be blended with an unmodified aromatic polycarbonate resin or another thermoplastic resin to be used as a modifier.

The modified aromatic polycarbonate resin of the present invention can be molded by any method such as an injection molding method, a compression molding method, an extrusion molding method and a solution casting method. The modified aromatic polycarbonate resin of the present invention includes, for example, additives such as a heat stabilizer, an antioxidant, a light stabilizer, a colorant, an antistatic agent, a lubricant, a release agent, and a glass fiber, if necessary. Inorganic fillers such as glass beads, carbon fibers, metal fibers, talc and silica can be added.

[0021]

EXAMPLES The present invention will be further described with reference to the following examples. The parts and% in the examples are parts by weight and% by weight, and the evaluation was performed by the following method. (a) Specific viscosity is 0.7 g of polymer and 100 ml of methylene chloride.
And was measured at 20 ° C. (b) The glass transition temperature was measured using DuPont DSC 910. (c) The total light transmittance was measured using Sigma 80 manufactured by Nippon Denshoku. (d) Melt fluidity (MFR) was measured according to JIS K 7210 using a semi-auto melt indexer manufactured by Toyo Seiki Co., Ltd. (e) Izod impact strength was measured according to JIS K 7110 (thickness 1/8 inch, with notch). (f) Tracking resistance was measured according to IEC 112.

Example 1 A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 316 parts of dried pyridine, 76 parts of bisphenol A was dissolved therein, and then the reaction of m-hydroxybenzyl alcohol and ε-caprolactone was carried out. 9.3 parts (molar ratio 1/5) and 2 parts of p-tert-butylphenol dissolved in 368.3 parts of dry methylene chloride and added, and 67.6 parts of phosgene (37.6 parts) at 15 to 20 ° C. with stirring.
It took 0 minutes and blew. 28 ~ 3 after phosgene blowing
The reaction was completed by stirring at 3 ° C. for about 1 hour. After the reaction was completed, the hydrochloride of pyridine formed was removed by filtration and poured into methanol to obtain a colorless polymer. The obtained polymer was again dissolved in 1300 parts of methylene chloride, washed with hydrochloric acid and washed with water repeatedly. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was evaporated to give a colorless polymer 90. 0.5 part was obtained (yield 96%). This polymer has a specific viscosity of 0.400, a glass transition temperature of 110 ° C.,
The proportion of the caprolactone portion was 9% by weight by IR absorption spectrum analysis, the MFR was 21 g / 10 min, and the total light transmittance was 89.
%, The Izod impact strength with notch was 76 kgcm / cm.

Example 2 The apparatus used in Example 1 was charged with 320 parts of dried pyridine, and 103.3 parts of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was added thereto. Was dissolved, 40.1 parts of a reaction product (mole ratio 1/20) of m-hydroxybenzyl alcohol and ε-caprolactone and 2 parts of p-tert-butylphenol were dissolved in 368.3 parts of methylene chloride and added. Under the same conditions as in Example 1, 39.6 parts of phosgene was blown in. After the completion of blowing phosgene, the same procedure as in Example 1 was carried out to obtain 144.9 parts of a polymer (yield: 95%). This polymer has a specific viscosity of 0.374, a glass transition temperature of 107 ° C, and the proportion of caprolactone moiety is 2 by IR absorption spectrum analysis.
6% by weight, MFR was 20 g / 10 minutes. 20% by weight of glass fiber chopped strand [3 PE-455 FB manufactured by Nittobo Co., Ltd.] was dry blended with this polymer, and the mixture was extruded into pellets by an extruder and injection-molded into a square plate having a thickness of 3 mm. The tracking resistance of this product is 2
It was 100 drops or more at 00V.

Comparative Example 1 The reaction product of m-hydroxybenzyl alcohol and ε-caprolactone was not used and p
82.2 parts polymer (yield 97%) in the same manner as in Example 1 except that the amount of -tert-butylphenol used was 1.8.
%) Was obtained. The specific viscosity of this polymer is 0.405, MFR
Was 11 g / 10 minutes, the total light transmittance was 90%, and the notched Izod impact strength was 85 kgcm / cm. 20% by weight of glass fiber chopped strand was dry-blended to this polymer in the same manner as in Example 2, and the tracking resistance was evaluated in the same manner as in Example 2. The variation was as large as 40 to 90 drops at 200V.

Comparative Example 2 105.3 parts of a polymer was obtained in the same manner as in Example 2 except that the reaction product of m-hydroxybenzyl alcohol and ε-caprolactone was not used (yield 94%). The specific viscosity of this polymer was 0.421, the glass transition temperature was high at 233 ° C., and MFR did not flow.

Example 3 The apparatus used in Example 1 was charged with 79 parts of dried pyridine, and bisphenol A was added thereto.
After dissolving 10.3 parts, a reaction product of m-hydroxybenzyl alcohol and ε-caprolactone (molar ratio 1/5)
38.2 parts and 0.6 part of p-tert-butylphenol were dissolved in 110.5 parts of dry methylene chloride and added, and 11.2 parts of phosgene was blown in under the same conditions as in Example 1.
After the completion of phosgene blowing, 48 parts (yield 94%) of a colorless polymer was obtained in the same manner as in Example 1. The specific viscosity of this polymer was 0.413, and the proportion of caprolactone moiety was 69% by weight by IR absorption spectrum analysis. This polymer 1
After uniformly dissolving 0 parts and 90 parts of the polymer synthesized in Comparative Example 2 in methylene chloride, the methylene chloride was evaporated to obtain a colorless polymer. The specific viscosity of this polymer is 0.40
7. Glass transition temperature was 141 ° C, proportion of caprolactone moiety was 7 wt% by IR absorption spectrum analysis, MFR was 18
g / 10 minutes, total light transmittance was 89%, and notched Izod impact strength was 80 kgcm / cm.

[0027]

EFFECTS OF THE INVENTION The modified aromatic polycarbonate resin of the present invention has improved melt fluidity and tracking resistance while maintaining the excellent transparency and mechanical properties of the aromatic polycarbonate depending on the amount of the modifying compound. Structural and functional materials for electrical components such as electrical and electronic parts, optical disks, optical lenses, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, evaporated plastic reflectors, displays, and binders of organic photoconductors. It is also extremely useful as a modifier for improving the melt flowability and tracking resistance of unmodified aromatic polycarbonate resins and other thermoplastic resins depending on the amount of the modifying compound.

Claims (1)

[Claims] 1. An aromatic polycarbonate resin comprising a dihydric phenol and a carbonate precursor is added to the following general formula [1]: [In the formula, R ₁ is a divalent aliphatic group which may contain an ether group having 1 to 10 carbon atoms, and R ₂ is 1 to 1 carbon atoms.
A monovalent aliphatic group or a halogen atom, m is an integer of 0 to 4, n is an integer of 1 to 100, and p is an integer of 0 to 4]. Group polycarbonate resin A modified aromatic polycarbonate resin containing 1 to 99% of the total number of structural units.