JPH09151309A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition containing an aromatic polycarbonate obtained by a fusion ester exchange method and an aromatic polyester, excellent in heat stability on its fusion and fire retarding property, and useful as an engineering plastic. SOLUTION: This resin composition contains (A) 1-99wt.% aromatic polycarbonate produced by a fusion ester exchange method and (B) 99-1wt.% aromatic polyester. Further, it is preferable that the component (A) is produced by a polymerization using a basic compound containing nitrogen or an alkali metal compound/alkaline earth metal compound as a catalyst, contains boric acid or boric acid ester and/or ammonium hydrogen phosphite, and has 3-60mol% terminal hydroxyl group concentration and also (C) 0.1-5wt.% one or more kinds of compounds of formula I and II [x1 to x6 are each H or a halogen; Y1 , Y3 are each sulfonic acid, Y2 , Y4 are each H or sulfonic acid; M1 and M2 are each an alkali (alkaline earth) metal; (n1 ), (n2 ) are 1, 2] as a fire retardant.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent heat resistance stability and flame retardancy when melted.

[0002]

Polycarbonate resin is an engineering plastic with excellent heat resistance, dimensional stability, mechanical strength, etc., used in electrical / home appliance parts, household products, precision / machine parts, office equipment parts, medical parts, sports parts, etc. It is used. However, polycarbonate resin
There are drawbacks in chemical resistance, economy (cost reduction), etc., and attempts have been made to improve these drawbacks by mixing with other resins and alloying.

Mixing polyethylene terephthalate or polybutylene terephthalate in order to improve the moldability of the polycarbonate resin and further enhance the chemical resistance has been disclosed in JP-A-48-54160 and JP-A-49-10.
7354.

However, the composition of the aromatic polyester resin and the aromatic polycarbonate resin as described above has a problem that the heat resistance stability at the time of melting in injection molding or film molding is lowered, and the flame retardancy is still improved. Not not.

In addition, A. Ballistreri is a journal of polymer
Science (Journal of Polymer S
Science, Vol. 26, 1988, it is pointed out that a resin obtained by adding a metal salt of benzenesulfonic acid to a polycarbonate has a lower resin temperature within a certain burning time than a resin not added. However, its detailed mechanism is not described. Further, the structure of polycarbonate (concentration of terminal hydroxyl groups) at that time is not mentioned at all.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent heat resistance stability and flame retardancy when melted.

[0007]

The present inventor has conducted various studies in order to solve the problems of the above-mentioned conventional aromatic polycarbonate resin compositions, and as a result, a specific aromatic sulfonic acid metal salt of 0.1% was obtained. ˜5% by weight and polymerized using a nitrogen-containing basic compound or an alkali metal compound / alkaline earth metal compound as a catalyst, and a terminal hydroxyl group containing boric acid or boric acid ester and / or ammonium hydrogen phosphite. The molten transesterification aromatic polycarbonate having a concentration of 3 mol% or more and less than 60 mol% undergoes thermal decomposition and cross-links more quickly when thermally deteriorated, and Char Formatio
Aromatic polycarbonate resin composition that causes n (char formation), exhibits adiabatic effect and oxygen barrier property, and is excellent in heat stability and flame retardancy when melted by mixing with aromatic polyester, especially polybutylene terephthalate The present invention has been completed by finding out that a product can be obtained.

That is, the first aromatic polycarbonate resin composition according to the present invention is an aromatic polycarbonate resin containing 1 to 99% by weight of a melt transesterification aromatic polycarbonate and 99 to 1% by weight of an aromatic polyester. It is a composition.

The second aromatic polycarbonate resin composition according to the present invention is polymerized using a nitrogen-containing basic compound or an alkali metal compound / alkaline earth metal compound as a catalyst, and boric acid or borate ester and / or An aromatic polycarbonate resin composition containing 1 to 99% by weight of a melt transesterification aromatic polycarbonate containing ammonium hydrogen phosphite and 99 to 1% by weight of an aromatic polyester.

Further, the third aromatic polycarbonate resin composition according to the present invention comprises 1 to 99% by weight of a melt transesterified aromatic polycarbonate having a terminal hydroxyl group concentration of 3 mol% or more and less than 60 mol% or a nitrogen-containing base. Polymerized by using a polar compound or an alkali metal compound / alkaline earth metal compound as a catalyst, containing boric acid or boric acid ester and / or ammonium hydrogen phosphite, and having a terminal hydroxyl group concentration of 3 mol% or more and less than 60 mol% An aromatic polycarbonate resin composition comprising 1 to 99% by weight of a melt transesterification aromatic polycarbonate and 99 to 1% by weight of an aromatic polyester. In addition, a fourth aspect according to the present invention
The aromatic polycarbonate resin composition is the above-mentioned first, second, or third aromatic polycarbonate resin composition containing a flame retardant.

Further, in the fifth aromatic polycarbonate resin composition according to the present invention, the flame retardant contains 0.1 to 5% by weight of a specific aromatic sulfonic acid metal salt. It is a 1st, 2nd, 3rd, or 4th aromatic polycarbonate resin composition.

The terminal hydroxyl group concentration of the melt-transesterified aromatic polycarbonate can be controlled by changing the charged molar ratio of the starting diaryl carbonate and the dihydroxy compound. For example, when an aromatic polycarbonate is produced by a melt transesterification method using bisphenol A and diphenyl carbonate as raw materials, the ends of the aromatic polycarbonate produced are a phenolic hydroxyl group derived from bisphenol A and a phenyl group derived from diphenyl carbonate. Become. Therefore, in the melt transesterification reaction, when the molar ratio of bisphenol A is increased, the terminal of the aromatic polycarbonate produced has a high phenolic hydroxyl group concentration,
On the contrary, when the molar ratio of diphenyl carbonate is increased, the phenyl group concentration of the end of the aromatic polycarbonate produced increases. Thus, the terminal concentration of the phenolic hydroxyl group can be freely controlled by changing the charged molar ratio of the raw materials.

According to the present invention, polymerization was carried out by a melt transesterification method using a nitrogen-containing basic compound or an alkali metal compound / alkaline earth metal compound as a catalyst, and contained boric acid or boric acid ester and / or ammonium hydrogen phosphite. When the terminal hydroxyl group concentration is 3 mol% or more and less than 60 mol%,
In addition, a melt transesterification aromatic carbonate containing a specific aromatic sulfonic acid metal salt as a flame retardant is mixed with an aromatic polyester, particularly polybutylene terephthalate, to produce butylene as a by-product by transesterification during kneading. Since the production of carbonate is suppressed, the heat resistance stability during melting is remarkably improved, and an aromatic polycarbonate resin composition having excellent flame retardancy can be obtained.

The aromatic polycarbonate used in the present invention contains a dihydroxy compound and a carbonic acid diester, a basic catalyst and an acidic substance for neutralizing the basic catalyst,
It is obtained by performing melt transesterification polycondensation.

Typical examples of the carbonic acid diester which is a raw material of the aromatic polycarbonate used in the present invention include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate and bis (biphenyl).
Examples thereof include carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Of these, diphenyl carbonate is particularly preferred.

Typical examples of the dihydroxy compound which is a raw material of the aromatic polycarbonate used in the present invention include:
2,2-bis- (4-hydroxyphenyl) propane,
2,2-bis- (4-hydroxyphenyl) butane,
2,2-bis- (4-hydroxyphenyl) -4-methylpentane, 4,4'-dihydroxy-2,2,2-triphenylethane, 2,2-bis- (4-hydroxyphenyl) octane, 2 , 2-bis- (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis-
(4-hydroxy-3-methylphenyl) propane,
2,2-bis- (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis- (4-hydroxy-
3-secondary butylphenyl) propane, 2,2-
Bis- (4-hydroxy-3-tert-butylphenyl) propane and the like can be mentioned.

Preferred basic catalysts that can be used in the production of the aromatic polycarbonate used in the present invention are at least one selected from nitrogen-containing basic compounds, alkali metal compounds and alkaline earth metal compounds. Can be mentioned. Here, the electron-donating amine compound is more preferable among the nitrogen-containing basic compounds, and among the alkali metal compounds and the alkaline earth metal compounds, borate salts of alkali metal compounds and borate salts of alkaline earth metal compounds are more preferable. .

Typical examples of the electron-donating amine compound include N, N-dimethyl-4-aminopyridine and 4- (4
-Methyl-1-piperidinyl) pyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, 2-hydroxypyridine, 4-hydroxypyridine, 2-aminopyridine, 4-aminopyridine, 2-methoxypyridine,
4-methoxypyridine, 2-methoxyimidazole, 2
-Dimethylaminoimidazole, 2-mercaptoimidazole, aminoquinoline, henzimidazole, imidazole, 2-methylimidazole, 4-methylimidazole, diazabicyclooctane (DABCO), 1,8
-Diaza-bicyclo [5,4,0] -7-undecene (DBU), 4- (4-methylpyrrolidinyl) pyridine and the like. Among these, the preferable one is
N, N-dimethyl-4-amino pyridine is mentioned.

Further, typical examples of the acid forming the counter ion of the electron-donating amine compound are carbonic acid, acetic acid, formic acid, nitric acid, nitrous acid, oxalic acid, sulfuric acid, phosphoric acid, fluoroboronic acid and hydrogenboronic acid. There is.

As typical examples of the alkali metal compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, Potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borate, lithium borate,
Potassium borate, sodium borohydride, lithium borohydride, potassium borohydride, sodium borohydride, sodium benzoate, potassium benzoate,
Lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, sodium salt of phenol, potassium salt, lithium salt and the like. However, alkali metal borate salts such as sodium borate, lithium borate and potassium borate and potassium acetate are preferably used. Particularly, lithium borate is preferable.

Typical examples of alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate,
Barium hydrogen carbonate, magnesium hydrogen carbonate, calcium carbonate, barium carbonate, strontium hydrogen carbonate, magnesium carbonate, strontium carbonate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, boric acid Examples thereof include magnesium, and among these, alkaline earth metal borate salts such as magnesium borate are preferable.

Boric acid and ammonium hydrogen phosphite can be used as the acidic substance for neutralizing the basic catalyst that can be used in the production of aromatic polycarbonate.
It may be one kind or a combination of two kinds.

The amount of the acidic substance added is required to be 0.01 to 500 times the molar amount of the catalyst used. When the basic catalyst is a nitrogen-containing basic compound, it is preferably 0.
The molar ratio is 01 to 10 times, and preferably 5 to 200 times when the basic catalyst is an alkali metal compound or an alkaline earth metal compound. If it is less than 0.01 times by mole, there is no effect on heat stabilization, and if it exceeds 500 times by mole, the degree of polymerization cannot be increased, which is not preferable.

The acidic substance may be added at the same time as the raw material monomer when the dihydroxy compound which is the raw material monomer, the carbonic acid diester and the transesterification catalyst is charged, and the relative viscosity of the polymer ( It may be added at any time when the polymer concentration of 0.5 g / dl, measured at 20 ° C. and methylene chloride concentration) reaches about 1.1 or more.

The ends of the aromatic carbonate obtained by the melt transesterification method using bisphenol A and diphenyl carbonate as raw materials are a phenolic hydroxyl group and a phenyl group. Here, the ratio of phenolic hydroxyl group terminals can be increased by increasing the ratio of the number of moles of diphenyl carbonate charged to the number of moles of bisphenol A used as a raw material. Thus, the phenolic hydroxyl group terminal concentration can be freely controlled by changing the charged molar ratio of the raw materials, but if the phenolic hydroxyl group terminal concentration exceeds 60 mol%, the hue and heat stability are deteriorated, which is not preferable. In addition, the phenolic hydroxyl terminal is 3
If the amount is less than mol%, thermal decomposition occurs more quickly upon heat deterioration to cause a cross-linking reaction, resulting in Char Formation, which makes it difficult to exhibit adiabatic effect and oxygen barrier property. Therefore, the hydroxyl group terminal of the polycarbonate resin obtained by the melt transesterification method used in the present invention is preferably 3 mol% or more and less than 60 mol%.

The specific aromatic sulfonic acid metal salt added to the above aromatic polycarbonate is represented by the following general formulas (I) and (II).

Embedded image (In the formula, X _{1 to} X ₆ : hydrogen or a halogen atom, Y ₁ , Y
₃ : Sulfonic acid group, Y ₂ , Y ₄ : hydrogen or sulfonic acid group, M ₁ , M ₂ : alkali metal or alkaline earth metal,
n _{1, n} 2: represents the integer of 1 or 2. In addition, X _{1 to} X ₆ ,
The substitution positions of Y ₃ and Y ₄ may be any of positions 1 to 8. ) One or more compounds selected from among the compounds represented by

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Typical examples of the metal salt of (di) sulfonic acid bonded to an aromatic ring include sodium salt, potassium salt, lithium salt of benzene (di) sulfonic acid, and naphthalene (di) sulfonic acid. Examples thereof include sodium salt, potassium salt, lithium salt, sodium salt of 2,4,5-trichlorobenzene (di) sulfonic acid, potassium salt, lithium salt, etc.
A range of from 5 to 5% by weight is preferred. If the amount is less than 0.1% by weight, the oxygen barrier property is not exerted, and if the amount exceeds 5% by weight, not only the fluidity is impaired, but also bleeding is caused and the physical properties are adversely affected.

The metal salt of (di) sulfonic acid bonded to the aromatic ring can be used alone or in combination of two or more kinds. Further, in the aromatic polycarbonate resin composition of the present invention, tris (2,4-di-t-butylphenyl) phosphite, 3,5-di-t-butyl-4-, is used as a stabilizer and an antioxidant. A phosphorus-based compound such as hydroxy-benzylphosphonate-diethyl ester and / or a hindered phenol-based compound can be mixed, and further, a metal salt of phosphoric acid, a metal salt of phosphorous acid and the like can be mixed.

In producing the aromatic polycarbonate resin composition of the present invention, the respective components can be mixed by a conventionally known method. For example, a method in which each component is dispersed and mixed by a turnable mixer, a Henschel mixer, a ribbon blender, a high speed mixer typified by a super mixer, and then melt-kneaded by an extruder, a Banbury mixer, a roll or the like is appropriately selected.

[0030]

EFFECT OF THE INVENTION Polymerization is carried out using a nitrogen-containing basic compound or an alkali metal compound / alkaline earth metal compound as a catalyst,
Boric acid or boric acid ester and / or ammonium hydrogen phosphite containing terminal hydroxyl group concentration of 3 mol% or more 60
By adding a specific aromatic sulfonic acid metal salt to a melt transesterified aromatic polycarbonate of less than mol% and mixing with an aromatic polyester, particularly polybutylene terephthalate, the heat stability during melting can be significantly improved. No, it can be flame retardant. In particular, it is considered that the incorporation of boric acid or boric acid ester and / or ammonium hydrogen phosphite suppresses the production of butylene carbonate produced as a by-product by transesterification with polybutylene terephthalate. Therefore, this resin composition is industrially useful due to its excellent heat resistance stability upon melting and flame retardancy.

[0031]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

First, a method for producing a melt-transesterified aromatic polycarbonate used in Examples is shown in (Synthesis Example 1). Furthermore, a method for measuring the viscosity average molecular weight of the produced melt transesterification aromatic polycarbonate, a method for calculating the terminal hydroxyl group concentration, and a melt fluidity which is a heat stability evaluation means during melting of the aromatic polycarbonate resin composition,
The test method for the deflection temperature under load and the change in thermogravimetricity is shown in (Test method).

(Synthesis Example 1) Method for producing aromatic polycarbonate by melt transesterification method: 2,2-bis (4-hydroxyphenyl) propane 22.8 kg (100 mol),
21.9 kg (102.5 mol) of diphenyl carbonate and 85 mg of lithium metaborate dihydrate (1 x 10
^-3 mol) aqueous solution, 1.0 g boric acid (2.4 x 10
^-2 mol) in a flask, melt at 180 ° C under nitrogen, stir well, gradually raise the pressure while reducing the pressure, and finally bring the temperature to 0.1 torr and 270 ° C. A unique aromatic polycarbonate was obtained. The viscosity average molecular weight was Mv = 23,000, and the terminal hydroxyl group concentration was 30 mol%.

(Test method) Viscosity average molecular weight: The intrinsic viscosity [η] of a methylene chloride solution at 20 ° C. was measured using an Ubbelohte viscometer, and the viscosity average molecular weight (Mv) was calculated using the following formula.

[Η] = 1.11 × 10 ⁻⁴ (Mv) ^0.82 Terminal hydroxyl group concentration: Measured by ¹³ C-NMR by measurement mode gated coupling, 114.80 p
The terminal hydroxyl group concentration was calculated from the ratio of pm and 129.50 ppm.

Melt fluidity: A melt indexer (L244 manufactured by TAKARA) was used, and measurement was performed under the following conditions.

Inner diameter: 1 mmφ, land length: 10 mm Measurement temperature: 280 ° C., load: 2160 g Deflection temperature under load: A test was conducted according to ASTM test method D648.

Thermogravimetric change (10% weight loss degree or degree of char formation) The pellets were measured using TG-DTA (differential thermal balance: Rigaku Denki Co., Ltd., standard type).

Example 1 2 parts by weight of 70 parts by weight of the melt transesterified aromatic polycarbonate resin obtained in Synthesis Example 1 was used.
After dry blending wt% metal salt of benzene sulfonic acid or metal salt of naphthalene sulfonic acid, after mixing with 30 parts by weight of polybutylene terephthalate (Duranex 2002: trademark, Polyplastics Co., Ltd.) in a Henschel mixer, a twin-screw extruder (PCM-3 manufactured by Ikemi Iron Works Co., Ltd.
0) was melt-kneaded and pelletized. Then, the pellets were dried at 80 ° C. for 5 hours and then retained at 280 ° C. for a predetermined time, and the melt index (melt flowability) was measured. Furthermore, from the resin composition retained at 280 ° C. for a predetermined time, an injection molding machine (name machine SJ45 / 70, mold temperature 50 ° C.)
Was used to prepare a test piece for measuring physical properties (ASTM dumbbell), and the deflection temperature under load was measured. The thermogravimetric change was measured on the pellets using TG-DTA (differential thermobalance: Rigaku Denki Co., Ltd., standard type). Table 1 shows the results.

[0040]

[Table 1] (Comparative Example 1) Phosgene-based aromatic polycarbonate resin (Iupilon S3000: trademark Mitsubishi Gas Chemical Co., Inc.)
2 parts by weight of benzene sulfonic acid metal salt or naphthalene sulfonic acid metal salt was dry blended with 70 parts by weight of polybutylene terephthalate (Duranex 20).
02: Trademark, manufactured by Polyplastics Co., Ltd.) with a Henschel mixer, and then melt-kneaded using a twin-screw extruder (PCM-30 manufactured by Ikemi Tekko KK) to form pellets. Then, after drying the pellets at 80 ° C. for 5 hours, 28
Melt index (melt flowability) was measured by allowing the mixture to stay at 0 ° C. for a predetermined time. Further, a test piece for physical property measurement (ASTM dumbbell) was prepared from the resin composition retained at 280 ° C. for a predetermined time by using an injection molding machine (name machine SJ45 / 70, mold temperature 50 ° C.), and the deflection temperature under load was measured. It was measured. Also,
The thermogravimetric change was measured on the pellets using TG-DTA (differential thermobalance: Rigaku Denki Co., Ltd., standard type). Table 2 shows the results.

[0041]

[Table 2] Comparative Example 2 The melt transesterification aromatic polycarbonate resin obtained in Synthesis Example 1 was measured in the same manner as in Comparative Example 1. The thermogravimetric change was measured on the pellets using TG-DTA (differential thermobalance: Rigaku Denki Co., Ltd., standard type). Table 3 shows the results.

[0042]

[Table 3] (Comparative Example 3) Polybutylene terephthalate (Duranex 2002: trademark, manufactured by Polyplastics Co., Ltd.) was used, and the same measurement as in Comparative Example 1 was performed. The thermogravimetric change was measured on the pellets using TG-DTA (differential thermobalance: Rigaku Denki Co., Ltd., standard type). Table 4 shows the results.

[0043]

[Table 4]

Claims (5)

[Claims] 1. An aromatic polycarbonate resin composition containing 1 to 99% by weight of an aromatic polycarbonate and 99 to 1% by weight of an aromatic polyester produced by a melt transesterification method. 2. The aromatic polycarbonate is polymerized by using a nitrogen-containing basic compound or an alkali metal compound / alkaline earth metal compound as a catalyst, and contains boric acid or boric acid ester and / or ammonium hydrogen phosphite. The aromatic polycarbonate resin composition described. 3. The aromatic polycarbonate resin composition according to claim 1, wherein the terminal hydroxyl group concentration of the aromatic polycarbonate is 3 mol% or more and less than 60 mol%. 4. The aromatic polycarbonate resin composition according to claim 1, 2 or 3, which contains a flame retardant. 5. The flame retardant contains 0.1 to 5% by weight of one or more compounds selected from compounds represented by the following general formulas (I) and (II). Alternatively, the aromatic polycarbonate resin composition according to claim 3 or 4. Embedded image (In the formula, X _{1 to} X ₆ : hydrogen or a halogen atom, Y ₁ ,
Y ₃ : a sulfonic acid group, Y ₂ , Y ₄ : hydrogen or a sulfonic acid group, M ₁ , M ₂ : an alkali metal or an alkaline earth metal,
n _{1, n} 2: represents the integer of 1 or 2. In addition, X _{1 to} X ₆ ,
The substitution positions of Y ₃ and Y ₄ may be any of positions 1 to 8. )