JP2003049059A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aromatic polycarbonate resin composition which is usable without remarkable changes in physical properties even in application under high temperature and humidity and has long life of its product and is excellent in safety. SOLUTION: This aromatic polycarbonate resin composition comprises 100 pts.wt. aromatic polycarbonate resin produced by transeterification and having >=12,000 viscosity-average molecular weight and 1-100 pts.wt. glass filler. The resin composition contains the terminal hydroxy group of the aromatic polycarbonate in an amount of <5 mol% based on total terminal groups.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing an aromatic polycarbonate resin and a glass filler, and more particularly to an aromatic polycarbonate resin composition having excellent weather resistance.

[0002]

2. Description of the Related Art Aromatic polycarbonate resin (PC resin) has excellent transparency, heat resistance and impact resistance, and is used in a wide range of fields such as automobile parts and structural materials such as building materials. Has been done. On the other hand, the aromatic polycarbonate resin has low rigidity as compared with glass, metal, etc., so in applications requiring high rigidity,
It was necessary to improve it by adding a suitable filler such as glass fiber. For example, Japanese Patent Laid-Open No. 2-24
In JP 7248, a PC resin produced by a transesterification method having a terminal hydroxyl group concentration of 5% or more with respect to the total number of terminal groups is kneaded with a glass filler, but the terminal hydroxyl group concentration is 5% or more. And the weather resistance such as moisture resistance and long-term heat aging characteristics was poor, and the strength of the molded product was significantly reduced. In recent years, the use of the above-mentioned materials under high temperature and high humidity conditions in Southeast Asia and the like has greatly increased, and there has been a demand for an aromatic polycarbonate resin composition having more excellent weather resistance than before.

[0003]

Accordingly, the present invention is intended to solve the problems associated with the prior art as described above, and aromatic compounds having improved weather resistance such as moisture resistance and long-term heat aging characteristics. It is intended to provide a polycarbonate resin composition.

[0004]

Means for Solving the Problems The present inventors have conducted diligent studies to find an aromatic polycarbonate resin composition having excellent weather resistance, and surprisingly found that an aromatic polycarbonate resin produced by a transesterification method was used. Then, it was found that the aromatic polycarbonate resin composition having excellent weather resistance can be obtained by making the concentration of the terminal hydroxyl group of the aromatic polycarbonate resin less than a specific amount, and the present invention has been completed. That is, the viscosity average molecular weight is 12,000.
Glass fillers 1 to 1 are added to 100 parts by weight of the aromatic polycarbonate resin produced by the above transesterification method.
The present invention relates to a resin composition containing 100 parts by weight of an aromatic polycarbonate resin in which the terminal hydroxyl groups of the aromatic polycarbonate resin are less than 5 mol% based on all the terminal groups.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The aromatic polycarbonate resin of the present invention is obtained by a transesterification reaction using an aromatic dihydroxy compound and a carbonic acid diester as raw materials in the presence of a transesterification catalyst. The aromatic dihydroxy compound used in the present invention is a compound having two aromatic hydroxyl groups in the molecule, and is preferably a compound represented by the following formula (1).

[0006]

[Chemical 1] Formula (1)

(In the formula, W is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, and 5 to 5 carbon atoms.
15 cycloalkylene group, cycloalkylidene group having 5 to 15 carbon atoms, or -O-, -S-, -CO-, -SO
-, - SO ₂ - those selected from the group consisting of divalent groups represented by, Y and Z are halogen or 1 carbon atoms
6 is a hydrocarbon group, p and q are integers of 0 to 2, and Y and Z, and p and q may be the same or different. )

Examples of the aromatic dihydroxy compound represented by the above formula (1) include bis (4-hydroxydiphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4). -Hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2, 2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxybiphenyl , 3,3 ', 5,5'-tetramethyl-4,4'-
Examples thereof include dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, and bis (4-hydroxyphenyl) ketone.
Particularly preferred is 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as "bisphenol A"). These aromatic dihydroxy compounds may be used alone or in combination of two or more. The carbonic acid diester used in the present invention is represented by the following general formula (2).

[0009]

[Chemical 2]

(In the formula, A and A'represent an aliphatic group having 1 to 18 carbon atoms or a substituted aliphatic group, an aromatic group or a substituted aromatic group, which may be the same or different.) The carbonic acid diester represented by the general formula (2) is
For example, dimethyl carbonate, diethyl carbonate, dialkyl carbonate compounds such as di-t-butyl carbonate, diphenyl carbonate, and substituted diphenyl carbonate such as ditolyl carbonate are exemplified, but diphenyl carbonate and substituted diphenyl carbonate are preferable, Diphenyl carbonate is particularly preferable. These carbonic acid diesters may be used alone or in combination of two or more.

In the present invention, a transesterification catalyst is used to obtain the aromatic polycarbonate resin.
As the catalyst, an alkali metal compound and / or an alkaline earth metal compound is used, and additionally, a basic boron compound, a basic phosphorus compound, a basic ammonium compound,
Alternatively, a basic compound such as an amine compound can be used in combination, but it is particularly preferable to use the alkali metal compound and / or the alkaline earth metal compound alone from the viewpoint of physical properties and handling.

The catalyst amount is aromatic dihydroxy
1 × 10 with respect to 1 mol of the compound^-8~ 5 x 10^-6Mole
It is preferably used in the range, more preferably 1 ×
10 ^-7~ 3 x 10^-6In the molar range, particularly preferably 2 ×
10^-7~ 2 x 10^-6Used in the molar range. This amount
If the amount is less, the molecular weight and the amount of terminal hydroxy groups are
Polymerization activity required to produce aromatic polycarbonate resins
If there is more than this amount, po
Limmer hue deteriorates, branching increases, polymer moldability
Tend to be compromised.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate and carbonic acid. Lithium, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, hydride Cesium boron, sodium phenyl boride, potassium phenyl boride, lithium phenyl boride, cesium phenyl boride, sodium benzoate, potassium benzoate, lithium benzoate,
Cesium benzoate, disodium hydrogen phosphate, 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 phenyl phosphate Cesium, sodium, potassium, lithium, cesium alcoholate, phenolate, bisphenol A
2 sodium salt, 2 potassium salt, 2 lithium salt, 2 cesium salt and the like. As the alkaline earth metal compound, for example, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, Magnesium carbonate, strontium carbonate,
Examples thereof include calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

Specific examples of the basic boron compound include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron and triethylphenyl. Boron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, sodium salts such as butyltriphenylboron, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, or strontium. Salt etc. are mentioned. Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine,
Alternatively, a quaternary phosphonium salt and the like can be mentioned.

Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide,
Trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltri Examples thereof include phenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide and the like.

Examples of amine compounds include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine,
2-hydroxypyridine, 2-methoxypyridine, 4-
Methoxypyridine, 2-dimethylaminoimidazole,
2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like can be mentioned. The transesterification reaction is generally carried out in a multi-step process of two or more steps. Specifically, the first
The reaction in the second step is carried out under reduced pressure of 9.3 × 10 ^{4 to} 1.33 × 10 ³ Pa at 120 to 260 ° C., preferably 180 to 240.
The reaction is carried out at a temperature of ° C for 0.1 to 5 hours, preferably 0.1 to 3 hours. Then, the reaction temperature is raised while increasing the pressure reduction degree of the reaction system, and finally, the pressure is reduced to 133 Pa or less under a reduced pressure of 24
The polycondensation reaction is performed at a temperature of 0 to 320 ° C. The reaction may be performed in a batch system, a continuous system, or a combination of a batch system and a continuous system, and the apparatus used may be a tank system, a tube system, or a column system.

The terminal hydroxyl group of the aromatic polycarbonate resin of the present invention is less than 5 mol% with respect to all the terminal groups,
Preferably less than 4.95 mol%, more preferably 4.95 mol%.
It is preferable to control it to less than 90 mol%. Here, the mol% of the terminal hydroxyl groups of the aromatic polycarbonate resin is determined by measuring the number of terminal hydroxyl groups (μeq / g) and the number of terminal phenyl groups (μeq / g) using ¹ H-NMR by a conventional method, The ratio of the number of hydroxyl groups can be calculated to obtain the terminal hydroxyl group concentration (mol%). When a resin composition with a glass filler is produced using an aromatic polycarbonate resin containing 5 mol% or more of terminal hydroxyl groups with respect to all terminal groups, the weather resistance such as moisture resistance and long-term heat aging characteristics is significantly deteriorated. There is a tendency. The lower limit of the ratio of terminal hydroxyl groups to all terminal groups is not particularly limited,
If it is extremely small, it is difficult to manufacture, so it is usually 0.5% or more, preferably 1% or more.

The proportion of terminal hydroxyl groups of the aromatic polycarbonate resin is influenced by the polymerization conditions such as the polymerization temperature, the degree of vacuum at the time of polymerization, the condenser temperature, etc., but under certain conditions, it is represented by bisphenol A. It can be controlled by the charging ratio of the aromatic dihydroxy compound and the carbonic acid diester typified by diphenyl carbonate. For example, when it is assumed that the above-mentioned respective factors are produced under the same conditions, and the obtained resin also has the same viscosity average molecular weight, the aromatic polycarbonate resin used for any application produced at any charging ratio. When the ratio of the terminal hydroxyl groups is 20%, an aromatic polycarbonate resin having a ratio of the terminal hydroxyl groups of less than 5 mol% based on all the terminal groups can be obtained by adjusting the charging ratio of the carbonic acid diester to the aromatic dihydroxy compound. It can be obtained by slightly increasing the charging ratio.

The viscosity average molecular weight of the aromatic polycarbonate resin in the present invention is 12,000 or more. It is preferably 13,000 or more, more preferably 15,
It is more than 000. Further, it is preferably 32,000 or less, more preferably 27,000 or less. If the viscosity average molecular weight is too low, sufficient strength as a composition cannot be obtained, and if it is too high, the melt fluidity during molding tends to decrease.

The glass filler used in the present invention is not particularly limited in kind, shape and the like, but for example, glass fiber, middle glass, glass flakes, glass beads and the like can be used. Of these, glass fiber is preferable. These glass fillers may be treated with, for example, a silane-based or titanate-based coupling agent, an aminosilane-based coupling agent, or an aminosilane-based coupling agent in order to improve adhesiveness. Specific coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane. Examples thereof include silane and γ-glycidoxypropylmethyldimethoxysilane.

In the present invention, the amount ratio of the aromatic polycarbonate resin to the glass filler is such that the glass filler is 1 to 100 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin.
Parts by weight, preferably 1 to 80 parts by weight of glass filler. If the compounding amount of the glass filler is more than 100 parts by weight, the melt flowability of the resin composition is poor and the moldability is deteriorated, whereas if it is less than 1 part by weight, the molded product cannot have rigidity, which is not preferable. .

Further, the resin composition of the present invention contains other resins and additives such as pigments, dyes, reinforcing agents, fillers, heat-resistant agents and oxidative deterioration-preventing when the resins are mixed and molded as long as the physical properties are not impaired. Agents, weathering agents, lubricants, release agents, crystal nucleating agents, plasticizers, fluidity improvers, antistatic agents and the like can be added. In producing the resin composition of the present invention, the respective components can be mixed by a conventionally known method. For example, a method may be selected in which each component is dispersed and mixed by a ribbon blender or a super mixer, and then melt-kneaded by an extruder or the like.

[0023]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples. The physical properties and evaluations of the aromatic polycarbonates obtained in the following examples were measured as follows. (1) Viscosity average molecular weight (Mv) The intrinsic viscosity of a 6 g / l methylene chloride solution was measured using an Ubbelohde viscometer, and the viscosity average molecular weight was determined by the following formula.

[Equation 1] [η] = 1.23 × 10 ⁻⁴ (Mv) ^0.83

(2) Ratio (mol%) of terminal hydroxyl groups in all terminal groups 0.02 g of a sample was dissolved in 0.4 ml of deuterated chloroform, and ¹ H-NMR (JNM-A manufactured by JEOL Ltd.) was performed at 30 ° C.
1400), the number of terminal hydroxyl groups (μeq / g) and the number of terminal phenyl groups (μeq / g) were measured, and the terminal hydroxyl group concentration (mol%) was calculated by the following formula.

## EQU2 ## Terminal hydroxyl group concentration (mol%) = ((number of terminal hydroxyl groups) / (number of terminal hydroxyl groups + number of terminal phenyl groups)) × 100 (3) Moisture resistance Aromatic polycarbonate resin compositions obtained in Examples and Comparative Examples 100g of product pellets at 65 ℃ / 85% RH
After the humidity resistance test for 2000 hours, the molecular weight of the aromatic polycarbonate resin was measured. That is, when the viscosity average molecular weight before the moisture resistance test is Mv1 and the viscosity average molecular weight after the moisture resistance test is Mv2, the moisture resistance retention rate (%) was calculated using the following formula.

[Equation 3] Moisture resistance retention rate (%) = (Mv2 / Mv1) × 100

(4) Long-term heat aging property In a bending test according to ASTM-D790, an initial bending elastic modulus (kgf / cm ² ) was measured, and the test piece was left for 2400 hours in a high temperature environment of 110 ° C. The flexural modulus retention rate was determined by measuring the flexural modulus.

Example 1 In a stainless steel 20 liter vertical stirring reactor equipped with a condenser, 2283 g (10.0 mol) of bisphenol A, 2356 g (11.0 mol) of diphenyl carbonate and 0.01 N sodium hydroxide as a catalyst. 0.7 ml (7 × 10 ⁻⁷ mol per 1 mol of bisphenol A) was charged and the atmosphere was replaced with nitrogen. This mixture was melted at 220 ° C. for 40 minutes to melt the raw material monomers, and then 220 ° C./1.33×10 ⁴ Pa
60 minutes, 240 ° C./2.00×10 ³ Pa for 60 minutes,
The reaction is performed at 280 ° C / 66.7 Pa for 60 minutes, and further,
2 wt ppm of butyl p-toluenesulfonate as a catalyst deactivator was added to the aromatic polycarbonate resin to terminate the reaction. As a result, the viscosity average molecular weight was 2100.
An aromatic polycarbonate resin having 0 and a terminal hydroxyl group concentration of 4% was obtained.

Obtained aromatic polycarbonate resin 10
0 parts by weight and glass fiber (manufactured by Asahi Fiber Glass Co., Ltd.,
Product name ECR glass fiber, fiber diameter 18μm, fiber length 4m
m) After mixing with 10 parts by weight using a blender, 30 m
It was melt-kneaded and pelletized by an m twin-screw extruder. Using the obtained pellets, a moisture resistance test was performed, the moisture resistance retention rate is shown in Table 1, and a bending test piece (ASTM test piece) was prepared by injection molding, and a long-term heat aging property test was performed to determine the bending elastic modulus. The retention rate is shown in Table 1.

Example 2 The reaction was carried out in the same manner as in Example 1 except that the amount of diphenyl carbonate was changed to 2367 g (11.05 mol), and the viscosity average molecular weight was 21,400 and the terminal hydroxyl group concentration was obtained. 2% of aromatic polycarbonate resin was obtained. Furthermore, it carried out similarly to Example 1, and mixed with glass fiber, and obtained the pellet. A moisture resistance test was conducted using the obtained pellets, and the moisture resistance retention rate is shown in Table 1.
Bending test pieces (ASTM test pieces) were prepared by injection molding, and a long-term heat aging property test was conducted. The bending elastic modulus retention rate is shown in Table 1.

[Example 3] The reaction was carried out in the same manner as in Example 1 except that the amount of diphenyl carbonate was changed to 2378 g (11.10 mol), and the viscosity average molecular weight was 21,500 and the terminal hydroxyl group concentration was obtained. 1% of aromatic polycarbonate resin was obtained. Furthermore, it carried out similarly to Example 1, and mixed with glass fiber, and obtained the pellet. A moisture resistance test was conducted using the obtained pellets, and the moisture resistance retention rate is shown in Table 1.
Bending test pieces (ASTM test pieces) were prepared by injection molding, and a long-term heat aging property test was conducted. The bending elastic modulus retention rate is shown in Table 1.

[Example 4] In Example 1, except that glass fibers were mixed in a ratio of 30 parts by weight to 100 parts by weight of the aromatic polycarbonate resin using a blender,
Mixed pellets were obtained in the same manner as in Example 1. Using the obtained pellets, a moisture resistance test was performed, the moisture resistance retention rate is shown in Table 1, and a bending test piece (ASTM test piece) was prepared by injection molding, and a long-term heat aging property test was performed to determine the bending elastic modulus. The retention rate is shown in Table 1.

[Comparative Example 1] The reaction was carried out in the same manner as in Example 1 except that the amount of diphenyl carbonate was changed to 2314 g (10.80 mol), and the viscosity average molecular weight was 21,000 and the terminal hydroxyl group concentration was obtained. 10% aromatic polycarbonate resin was obtained. Furthermore, in the same manner as in Example 1,
Mixed with glass fiber to obtain pellets. A moisture resistance test was conducted using the obtained pellets, and the moisture resistance retention rate was shown in Table 1.
Bending test piece (ASTM test piece) by injection molding
Was prepared and subjected to a long-term heat aging property test, and the flexural modulus retention is shown in Table 1.

[Comparative Example 2] The reaction was carried out in the same manner as in Example 1 except that the amount of diphenyl carbonate was changed to 2271 g (10.60 mol), and the viscosity average molecular weight was 21,300 and the terminal hydroxyl group concentration was obtained. 20% of aromatic polycarbonate resin was obtained. Furthermore, in the same manner as in Example 1,
Mixed with glass fiber to obtain pellets. A moisture resistance test was conducted using the obtained pellets, and the moisture resistance retention rate was shown in Table 1.
Bending test piece (ASTM test piece) by injection molding
Was prepared and subjected to a long-term heat aging property test, and the flexural modulus retention is shown in Table 1.

[Comparative Example 3] In Comparative Example 1, except that 100 parts by weight of the aromatic polycarbonate resin was mixed with 30 parts by weight of glass fiber using a blender,
Mixed pellets were obtained in the same manner as in Comparative Example 1. Using the obtained pellets, a moisture resistance test was performed, the moisture resistance retention rate is shown in Table 1, and a bending test piece (ASTM test piece) was prepared by injection molding, and a long-term heat aging property test was performed to determine the bending elastic modulus. The retention rate is shown in Table 1.

[0034]

[Table 1]

[0035]

INDUSTRIAL APPLICABILITY The aromatic polycarbonate resin composition of the present invention can be used without being markedly changed in physical properties even in applications where it is exposed to high humidity and high temperature conditions.
It can extend the life of the product and contribute to safety. Therefore, it is extremely useful for various applications such as automobile parts, building material parts, electric / electronic parts, etc. and greatly contributes to the industrial world.

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Claims (3)

[Claims] 1. An aromatic polycarbonate resin 1 having a viscosity average molecular weight of 12,000 or more and produced by a transesterification method.
A resin composition containing 1 to 100 parts by weight of a glass filler with respect to 00 parts by weight, and containing an aromatic polycarbonate resin in which the terminal hydroxyl groups of the aromatic polycarbonate resin are less than 5 mol% with respect to all the terminal groups. An aromatic polycarbonate resin composition comprising: 2. The aromatic polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate resin is a resin produced by a transesterification method of an aromatic dihydroxy compound and a carbonic acid diester. 3. The aromatic polycarbonate resin is 2,2-
The aromatic polycarbonate resin composition according to claim 1, which is a resin produced by a transesterification method of bis (4-hydroxyphenyl) propane and diphenyl carbonate.