JPH07118514A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. having a good transparency by compounding an arom. polycarbonate resin formed using a reaction product of a specific alcohol with a lactone as the terminal stopper with a glass filler having a refractive index close to that of the resin. CONSTITUTION:A reaction product represented by the formula wherein R is a 1-10C aliph. hydrocarbon group optionally having an ether bond; R' is a 1-10C aliph. hydrocarbon group or halogen; m is 4-20; n is 2-100; and p is 0-4 is obtd. by mixing and thermaly polymerizing an optionally substd. hydroxyaralkyl alcohol (e.g. 2-hydroxybenzyl alcohol) with a lactone. A terminal stopper contg. the reaction product in an amt. of at least 45mol% is added to the reaction product of a dihydric phenol with phosgene, etc., giving an arom. polycarbonate resin. 40-95 pts.wt. resin obtd. as above is compounded with 5-60 pts.wt. glass fiber which has a refractive index different from that of the resin by up to 0.01, and the resulting compsn. is pelletized by melt extrusion, giving the title compsn.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aromatic polycarbonate resin composition. More specifically, it relates to a glass-filler-containing aromatic polycarbonate resin composition having excellent transparency.

[0002]

2. Description of the Related Art 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A), which is conventionally known as a typical aromatic polycarbonate resin, is supplemented with a carbonate precursor such as phosgene or diphenyl carbonate. The bisphenol A polycarbonate resin obtained by the reaction is used in many fields because it is excellent in transparency, heat resistance, dimensional accuracy and the like. It is also known to add a glass-based filler such as glass fiber in order to further improve rigidity and dimensional stability. However, when a glass-based filler is added, there is a problem that the transparency, which is an excellent characteristic of the aromatic polycarbonate resin, is significantly reduced. While this has a refractive index of about 1.585 for a typical aromatic polycarbonate resin,
The refractive index of glass used for glass fiber is about 1.5.
This is because there is a large difference of about 45 from 45. As a method for solving this problem, a method using glass having a relatively high refractive index (Japanese Patent Laid-Open No. 49-47408, Japanese Patent Laid-Open No. 6-47408)
No. 2-1338) has been proposed. However, these methods have not yet yielded satisfactory results.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic polycarbonate resin composition containing a glass-based filler such as glass fiber, glass powder and glass beads having improved transparency.

The inventor of the present invention intends to achieve the above object.
As a result of extensive research on modification of aromatic polycarbonate resin, a glass-based filler having a small difference in refractive index from the aromatic polycarbonate resin was used, and a monohydric phenol having a specific structure was used in a specific amount as a terminal stopper. It has been found that the object of the present invention can be achieved by using a specific aromatic polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor. The present invention has been completed based on this finding.

[0005]

According to the present invention, at least 45 mol% of the terminal stopper is represented by the following general formula [1].

[0006]

[Chemical 2]

[Wherein R is an aliphatic hydrocarbon group having 1 to 10 carbon atoms and optionally containing an ether group, R'is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, m is an integer of 4 to 20, n is an integer of 2 to 100, and p is an integer of 0 to 4. ] 40 to 95% by weight of an aromatic polycarbonate resin using a reaction product of a substituted or unsubstituted hydroxyaralkyl alcohol and a lactone, and a difference in refractive index between the aromatic polycarbonate resin and the aromatic polycarbonate resin is 0.
The present invention relates to an aromatic polycarbonate resin composition containing 60 to 5% by weight of a glass-based filler having a content of 01 or less.

The aromatic polycarbonate resin used in the present invention is obtained by reacting at least one dihydric phenol with a carbonate precursor by using an end-stopper having a specific structure represented by the above general formula [1]. It is a specific aromatic polycarbonate resin obtained by.

The terminal terminating agent represented by the above general formula [1] used here is a reaction of an alcohol group with a lactone and ring-opening of a lactone by mixing and heating a substituted or unsubstituted hydroxyaralkyl alcohol and a lactone. It is produced by a polymerization reaction. The degree of polymerization (n) of the lactone can be arbitrarily controlled by adjusting the molar ratio of the lactone and the hydroxyaralkyl alcohol. If the degree of polymerization of the lactone becomes too large, the reactivity with phenol will decrease, so 2-100 is suitable.

Examples of the substituted or unsubstituted hydroxyaralkyl alcohol used here include 2-hydroxybenzyl alcohol, 3-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-hydroxy) Phenyl) 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-hydroxyphenyl) hexanol-2, 4- (4-hydroxyphenyl) hexanol-3, etc. Used.

The lactone is a lactone having 5 to 21 carbon atoms, and the 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-
δ-valerolactone, ε-caprolactone, monomethyl-ε-caprolactone, monoethyl-ε-caprolactone and the like can be mentioned. Particularly, δ-valerolactone and ε-caprolactone are preferable.

Although a part of the above-mentioned terminal stopper may be replaced with another terminal stopper, if the amount of the terminal stopper used is too small, the transparency of the obtained resin composition cannot be sufficiently improved. Therefore, it is necessary to use at least 45 mol% of the total amount of the terminal stopper. Examples of other end terminators include monofunctional phenols such as phenol, p-tert-butylphenol, p-cumylphenol, and isooctylphenol.

Examples of the dihydric phenol include hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane and 1,1-
Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bisphenol A, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1, 1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 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'- Hydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl oxide, 9,9-bis (4-hydroxyphenyl) fluorene , 1,3-bis (4-hydroxyphenyl)-
5,7-dimethyladamantane and the like are mentioned, and among them, bisphenol A, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl. Cyclohexane,
1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane is preferred. These may be used alone or in combination of two or more kinds, 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 copolymerized.

Examples of the carbonate precursor include phosgene, phosgene dimer, phosgene trimer, and bischloroformate of the above dihydric phenols. Among them, phosgene is preferable.

To produce an aromatic polycarbonate resin from the above-mentioned dihydric phenol, carbonate precursor and terminal stopper, a method used for producing an ordinary aromatic polycarbonate resin, for example, dihydric phenol with a carbonate precursor such as phosgene is used. It is manufactured by a reaction method. The reaction between the dihydric phenol and phosgene is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to accelerate the reaction. The reaction temperature is usually 0 to 40 ° C, and the reaction time is several minutes to 5
Usually, it is preferable to keep the pH during the reaction at 10 or higher.
If the molecular weight of the aromatic polycarbonate resin thus obtained is too small, it becomes brittle, so that the specific viscosity is preferably 0.23 or more.

The glass-based filler used in the present invention has a difference in refractive index from the aromatic polycarbonate resin of 0.01 or less,
It is preferably 0.005 or less. Refractive index difference is 0.0
When it exceeds 1, the transparency is deteriorated. Its shape is, for example, fibrous, powdery, flake-shaped, plate-shaped, or any other shape that is generally applicable to thermoplastic resins. In the case of fibrous material, a diameter of about 3 to 25 μm is preferable. The inside fiber length is preferably about 0.02 to 0.5 mm. Further, the glass-based filler is subjected to a surface treatment such as a silane coupling agent for the purpose of improving the affinity with the resin,
Focusing treatment may be performed with an epoxy resin, an acrylic resin, a urethane resin, or the like for the purpose of improving handleability. The addition ratio of the glass-based filler is 5 to 60% by weight, preferably 1
It is 0 to 55% by weight. If it is less than 5% by weight, it is difficult to obtain a sufficient glass-reinforcing effect, and if it exceeds 60% by weight, moldability is deteriorated, which is not suitable.

Any method may be employed to produce the glass-filler-containing resin composition of the present invention. For example, a tumbler containing an aromatic polycarbonate resin and a glass-based filler,
Any method such as dry blending using a super mixer or Nauta mixer and then pelletizing with an extruder, a method of preliminarily mixing an aromatic polycarbonate resin and other additives, and then extruding with glass fiber to pelletize may be used. Further, the resin composition containing a glass-based filler of the present invention can be molded by any method such as an injection molding method, a compression molding method and an extrusion molding method.

The aromatic polycarbonate resin composition of the present invention may contain a phosphorus-based heat stabilizer, an antioxidant, etc., if necessary. Examples of phosphorus-based stabilizers include triphenylphosphite, trisnonylphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, Didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-
4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-diphenyl) -Tert-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-tert
-Butylphenyl) -4,4-diphenylenephosphonite and other phosphorous acid triesters, diesters, and monoesters, which may be used alone or in combination of two or more. Examples of phenolic antioxidants include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3- (3,5).
-Di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3-
(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N- Hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,3
5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis {1,1-dimethyl-2-
[Β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4
8,10-tetraoxaspiro (5,5) undecane and the like can be mentioned, and the preferable addition amount is 0.00005 to 0.0.
It is about 5% by weight. If desired, higher fatty acid esters of polyhydric alcohols can be added, and preferred fatty acid esters are all esters of saturated aliphatic monocarboxylic acids having 8 to 22 carbon atoms with glycols, glycerol, pentaerythritol and the like. , Partial ester, etc., and the preferable addition amount is 0.001 to 0.2% by weight.
It is a degree. Further, additives such as a light stabilizer, a colorant, an antistatic agent and a lubricant can be added, and another polycarbonate resin or another thermoplastic resin can be blended.

[0019]

EXAMPLES The present invention will be further described below with reference to examples. The parts and% in the examples are parts by weight and% by weight, and the specific viscosity is 0.7 g of polymer and 100 ml of methylene chloride.
It was dissolved in and measured at 20 ° C, and the refractive index was measured at 25 ° C using an Abbe refractometer. The haze value was measured using Nippon Denshoku Sigma 80.

[0020]

[Synthesis Example 1] 4206.2 parts of ion-exchanged water and 295.2 parts of 48% sodium hydroxide aqueous solution were put into a reactor equipped with a thermometer, a stirrer and a reflux condenser, and bisphenol A81 was added.
After dissolving 1.7 parts and 0.95 parts of hydrosulfite, 2589.4 parts of methylene chloride were added, and the mixture was stirred for 15 minutes.
387.5 parts of phosgene were bubbled in at -20 ° C over 60 minutes. After blowing phosgene, the reaction product of m-hydroxybenzyl alcohol and ε-caprolactone (molar ratio 1/2
0) 487.8 parts was dissolved in 800 parts of methylene chloride and added, and then 148.5 parts of a 48% sodium hydroxide aqueous solution and 79.2 parts of bisphenol A were added to emulsify and then 2.5 parts of triethylamine was added. Then 28-33 ° C
The reaction was completed by stirring for about 2 hours. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was evaporated to give colorless polymer 13.
21.4 parts were obtained (yield 95%). The ratio of polycaprolactone portion of this polymer was 3 by IR absorption spectrum analysis.
It was 4.3% by weight, the specific viscosity was 0.355, and the refractive index was 1.580.

[0021]

[Synthesis Example 2] Ion-exchanged water 17 was added to the same apparatus as in Synthesis Example 1.
800 parts and 3732 parts of 48% sodium hydroxide aqueous solution were charged, and 1,1-bis (4-hydroxyphenyl)-
After dissolving 3,131 parts of 3,3,5-trimethylcyclohexane, 11110 parts of methylene chloride was added, and 1200 parts of phosgene was blown into the reaction mixture at 20 ° C. for about 40 minutes with vigorous stirring to cause a reaction. Then raise the internal temperature to 30 ℃ and m
420.6 parts of a reaction product of -hydroxybenzyl alcohol and ε-caprolactone (molar ratio ⅕) was added, and after emulsification, 3.5 parts of triethylamine was added and stirring was continued for 2 hours to complete the reaction. After completion of the reaction, the same treatment as in Synthesis Example 1 was carried out to obtain a polymer (yield 99.5%). The proportion of polycaprolactone portion in this polymer was 9.7% by weight by IR absorption spectrum analysis, the specific viscosity was 0.339, and the refractive index was 1.553.

[0022]

[Synthesis Example 3] Ion-exchanged water 42 was added to the same apparatus as in Synthesis Example 1.
06.2 parts and 48% aqueous sodium hydroxide solution 295.
After 2 parts were charged and 811.7 parts of bisphenol A was dissolved, 2589.4 parts of methylene chloride was added, and 387.5 parts of phosgene was blown into the reaction mixture at 20 ° C. for about 40 minutes while stirring vigorously. Then raise the internal temperature to 30 ℃ and p-
After 30.4 parts of tert-butylphenol was added and emulsified, 2.5 parts of triethylamine was added and stirring was continued for 2 hours to complete the reaction. After completion of the reaction, the same treatment as in Synthesis Example 1 was carried out to obtain a polymer (yield 99%). The polymer had a specific viscosity of 0.293 and a refractive index of 1.585.

[0023]

[Synthesis Example 4] m-hydroxybenzyl alcohol and ε-
A polymer was obtained in the same manner as in Synthesis Example 2 except that 90.9 parts of p-tert-butylphenol was used instead of the reaction product of caprolactone (yield 99%). This polymer had a specific viscosity of 0.248 and a refractive index of 1.556.

[0024]

Example 1 80.0 parts of the polymer obtained in Synthesis Example 1 was mixed with 20.0 parts of a glass fiber having an index of refraction of 1.579 (average fiber diameter: 24 μm, average fiber length: 6 mm), and the extruder [NAKATANI Co., Ltd. ) Manufactured by VSK-30) at a cylinder temperature of 260 ° C. and pelletized. This pellet is injection molded [Nestal Cycap 4 manufactured by Sumitomo Heavy Industries, Ltd.
80/150], a test piece of 50 mm × 50 mm × 2 mm was prepared at a cylinder temperature of 290 ° C. and a mold temperature of 90 ° C., and the haze value was measured to be 17%.

[0025]

Example 2 To 80.0 parts of the polymer obtained in Synthesis Example 2 was added 20.0 parts of glass fiber having an index of refraction of 1.545 (average fiber diameter 13 μm, average fiber length 3 mm) and tested in the same manner as in Example 1. A piece was prepared and the haze value was measured and found to be 19%.

[0026]

Comparative Example 1 80.0 parts of the polymer obtained in Synthesis Example 3 and 20.0 glass fibers having a refractive index of 1.579 used in Example 1 were used.
Part was added, a test piece was prepared in the same manner as in Example 1, and the haze value was measured and found to be 41%.

[0027]

Comparative Example 2 80.0 parts of the polymer obtained in Synthesis Example 4 and 20.0 glass fiber having a refractive index of 1.545 used in Example 2 were used.
Part was added, a test piece was prepared in the same manner as in Example 1, and the haze value was measured and found to be 54%.

[0028]

The glass-filler-containing aromatic polycarbonate resin composition of the present invention has improved transparency and is therefore very suitably used in the fields of automobile parts, building materials, electric / electronic parts and the like.

Claims (1)

[Claims] 1. At least 45 mol% of the terminal stopper is represented by the following general formula [1]: [In the formula, R is an aliphatic hydrocarbon group which may contain an ether group having 1 to 10 carbon atoms, and R'is 1 to 1 carbon atoms.
10 aliphatic hydrocarbon groups or halogen atoms, m is 4 to 2
0 is an integer, n is an integer of 2 to 100, and p is an integer of 0 to 4. ] 40 to 95% by weight of an aromatic polycarbonate resin using a reaction product of a substituted or unsubstituted hydroxyaralkyl alcohol and a lactone, and a glass having a difference in refractive index of 0.01 or less with the aromatic polycarbonate resin. An aromatic polycarbonate resin composition comprising 60 to 5% by weight of a filler.