JP3230969B2 - Aromatic polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a material having excellent properties such as weld strength, heat stability and flame retardancy.
The present invention relates to a thermoplastic resin composition having an excellent balance of physical properties such as impact resistance, moldability, and rigidity.

[0002]

2. Description of the Related Art Polycarbonate resin is an engineering plastic with excellent heat resistance, dimensional stability, mechanical strength, etc., used in electrical and home appliance parts, precision and mechanical parts, office equipment parts, medical parts, household goods, sports parts, etc. It is used. However, polycarbonate resin has moldability,
There are drawbacks in chemical resistance, economy (cost reduction), plating properties, etc., and attempts have been made to improve these drawbacks by mixing with other resins, alloying, and the like. In particular, attempts to improve the moldability of the polycarbonate resin and further reduce the thickness dependency of the impact strength have been made by adding ABS resin (acrylonitrile-butadiene-styrene polymer) or MB to the polycarbonate resin.
S resin (methyl methacrylate-butadiene-styrene polymer) was mixed (JP-B-38-15).
Nos. 225, 39-71, 42-11496, and 51-11142). However, since the ABS resin or MBS resin mixed with the polycarbonate resin contains a graft polymer containing a diene rubber, the synthesized thermoplastic resin composition has poor weld strength, weather resistance, and heat stability. Had the disadvantage that

Further, Japanese Patent Application Laid-Open No. Hei 2-261852 discloses an invention in which the weld strength of a molded article of a resin composition containing an aromatic polycarbonate and an aromatic vinyl-diene-vinyl cyanide copolymer (ABS resin) is improved. However, even in the present invention, the disadvantages of flame retardancy and heat stability have not been improved yet.

Further, A.I. Ballistreri is a journal of polymer science (Journal of Polymer S)
26, 1988, point out that a resin obtained by adding a metal salt of benzenesulfonic acid to polycarbonate has a lower resin temperature within a certain burning time than a resin not added. However, its detailed mechanism is not described. Also, no mention is made of the structure (terminal hydroxyl group concentration) of the polycarbonate at that time.

[0005]

SUMMARY OF THE INVENTION The present invention has excellent properties in weld strength, flame retardancy, and heat stability.
An object of the present invention is to provide an aromatic polycarbonate resin composition mixed with a non-halogen flame retardant, which is excellent in physical properties such as appearance, impact resistance, moldability and rigidity.

[0006]

The present inventor has conducted various studies to solve the above-mentioned problems of the aromatic polycarbonate resin composition. As a result, the specific aromatic sulfonic acid metal salt was added in an amount of 0.1 to 5% by weight. % Mixed hydroxy esterified aromatic polycarbonate having a terminal hydroxyl group concentration of 3 mol% or more and less than 60 mol% thermally decomposes more quickly at the time of thermal degradation to cause a cross-linking reaction, thereby causing CharFormation (char formation). Shows oxygen barrier properties. Further, a rubber-modified styrene resin and an acrylonitrile-styrene copolymer are added to a melt transesterification aromatic polycarbonate having a terminal hydroxyl group concentration of 3 mol% or more and less than 60 mol% in which an aromatic sulfonic acid metal salt is mixed at 0.1 to 5% by weight. The present inventors have discovered that an aromatic polycarbonate resin composition having excellent weld strength, flame retardancy, and heat stability can be obtained by mixing, and completed the present invention. That is, the first aromatic polycarbonate resin composition according to the present invention is produced by a melt transesterification method and has a terminal hydroxyl group concentration of 3 mol% or less.
Above 60 below mol% der Ru aromatic polycarbonate 10
An aromatic polycarbonate resin composition containing 90% by weight and 90 to 10% by weight of a mixture of a rubber-modified styrenic resin and an acrylonitrile-styrene copolymer.
Qualitatively contains aromatic phosphate esters and fibrous reinforcement
In addition, as a flame retardant, the following general formula (I) or (II)
At least one compound selected from the compounds represented by
Contains .

Embedded image ( Wherein , X _{1 to} X ₆ : hydrogen or 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 an integer of 1 or 2. Note that X _{1 to} X ₆ , Y ₃ , Y ₄
May be in any of positions 1 to 8. )

Further, the second aromatic polycarbonate resin composition according to the present invention comprises the first aromatic polycarbonate resin.
In the resin composition, the aromatic polycarbonate produced by the above-mentioned melt transesterification method 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 Aroma containing ammonium hydrogen phosphite
It is an aromatic polycarbonate resin composition .

Further, Fang aromatic polycarbonate resin composition, the above general formula (I) or aromatic sulfonic acid metal compound as a specific flame retardant represented by (II) 0.1 to 5
It may contain% by weight.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As a typical example of the metal salt of (di) sulfonic acid bonded to an aromatic ring, which is the compound represented by the above general formulas (I) and (II) in the present invention,
Sodium, potassium and lithium salts of benzene (di) sulfonic acid, sodium, potassium and lithium salts of naphthalene (di) sulfonic acid, sodium and potassium salts of 2,4,5-trichlorobenzene (di) sulfonic acid Salts, lithium salts and the like can be mentioned, but the amount of addition is preferably in the range of 0.1 to 5% by weight based on the polycarbonate. If the content is less than 0.1% by weight, there is no oxygen barrier property effect, and
If the content exceeds 10% by weight, not only does the fluidity deteriorate, but it bleeds and adversely affects the physical properties. The metal salt of (di) sulfonic acid bonded to the aromatic ring can be used alone or in combination of two or more.

[0010] Specific examples of the rubber-modified styrene resin used in the present invention include polybutadiene, butadiene copolymer, ethylene, propylene copolymer rubber, and the like.
Ethylene-propylene-diene copolymer rubber, alkyl acrylate polymer elastomer, alkyl acrylate copolymer elastomer and ethylene
The glass transition temperature selected from the vinyl acetate copolymer is -1
Elastomers at 0 ° C. or lower can be mentioned. Styrene, α-methylstyrene, p-methylstyrene, and the like can be used as the styrene component.

The aromatic polycarbonate used in the present invention is obtained by adding a dihydric phenol and a carbonic acid diester to a basic catalyst and adding an acidic substance that neutralizes the basic catalyst,
It is obtained by performing melt transesterification polycondensation.

Representative examples of the carbonic diester as 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, bis (biphenyl).
Examples include carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like. Of these, diphenyl carbonate is particularly preferred.

Representative examples of the dihydric phenol which is a raw material of the aromatic polycarbonate used in the present invention include 2,2.
2-bis- (4-hydroxyphenyl) propane, 2,
2-bis- (4-hydroxyphenyl) butane, 2,2
-Bis- (4-hydroxyphenyl) -4-methylpentane, 2,2-bis- (4-hydroxyphenyl) octane, 4,4'-dihydroxy-2,2,2-triphenylethane, 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-secondarybutylphenyl) propane, 2,2-bis-
(4-hydroxy-3-tert-butylphenyl)
And propane.

The basic catalyst which can be used in the production of the aromatic polycarbonate used in the present invention includes, for example, one or more selected from nitrogen-containing basic compounds, alkali metal compounds and alkaline earth metal compounds. Among them, a nitrogen-containing basic compound and a borate of an alkali metal compound or an alkaline earth metal compound are preferable.

A typical example of the electron donating amine is 4-
(4-methyl-1-piperidinyl) pyridine, N, N-
Dimethyl-4-aminopyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, 4-aminopyridine, 2-aminopyridine, 2-hydroxypyridine, 2
-Methoxypyridine, 4-methoxypyridine, 4-hydroxypyridine, 2-dimethylaminoimidazole, 2
-Methoxyimidazole, 2-mercaptoimidazole, aminoquinoline, benzimidazole, imidazole, 2-methylimidazole, 4-methylimidazole, diazabicyclooctane (DABCO), 1,8-
Diaza-bicyclo [5,4,0] -7-undecene (D
BU), 4- (4-methylpyrrolidinyl) pyridine and the like.

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

Representative examples of the alkali metal compound include 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, dipotassium salt of bisphenol A, dilithium salt, phenol sodium salt, potassium salt, lithium salt, etc. Preferably, alkali metal borates such as sodium borate, lithium borate and potassium borate and potassium acetate are used.

Representative examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate,
It is desirable that the hydroxyl terminal of barium hydrogencarbonate, magnesium hydrogencarbonate, strontium hydrogencarbonate, calcium carbonate, and the polycarbonate resin obtained by the transesterification method be 3 mol% or more and less than 60 mol%.

The following general formulas (I) and (II)

Embedded image (Wherein, 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 an integer of 1 or 2. Note that X _{1 to} X ₆ ,
The substitution position of Y ₃ and Y ₄ may be any of 1 to 8 positions. Representative examples of the metal salt of (di) sulfonic acid bonded to an aromatic ring, which is a compound represented by the following formulas: sodium, potassium, lithium, and naphthalene (di) sulfonic acid of benzene (di) sulfonic acid Sodium salt, potassium salt, lithium salt, sodium salt, potassium salt, lithium salt of 2,4,5-trichlorobenzene (di) sulfonic acid, and the like.
A range of 1 to 5% by weight is preferred. If it is less than 0.1% by weight, there is no effect of the oxygen barrier property, and if it exceeds 5% by weight, not only does the fluidity deteriorate, but it also bleeds and adversely affects the physical properties. The metal salt of (di) sulfonic acid bonded to the aromatic ring can be used alone or in combination of two or more.

Further, the aromatic polycarbonate resin composition of the present invention comprises a heat stabilizer, an antioxidant, a hindered phenol, a phosphite compound, a phosphonite compound, a metal phosphate, a metal phosphite, and the like. Can also be added.

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

[0022]

The resin composition of the present invention is a thermoplastic resin composition having excellent well strength, flame retardancy and heat resistance stability by incorporating a non-halogen type flame retardant into a melt transesterification polycarbonate and a styrene resin. It is.

[0023] by a conventional method to give a polycarbonate over preparative (Synthesis Example 1 and 2). Polycarbonate obtained in Synthesis Example 1
The viscosity average molecular weight of the nate is Mv = 23,000,
The terminal hydroxyl group concentration was 30 mol%. Obtained in Synthesis Example 2
The viscosity average molecular weight of the polycarbonate obtained was Mv = 24,
000, and the terminal hydroxyl group concentration was 18 mol%.

Thermogravimetric Change (10% Weight Reduction or Char Degree) The pellets were measured using TG-DTA (differential thermobalance: Rigaku Denki Co., standard type).

The evaluation test of the aromatic polycarbonate resin composition was performed as follows. Irradiation test: Using a sunshine weather meter. 400 hours, AST
Irradiate the M dumbbell. Tensile strength: according to ASTM test method D638. Flexural strength: ASTM test method D79
According to 0. Deflection temperature under load: ASTM test method D6
According to 48. Heat aging test: A test piece of a polycarbonate resin composition having a thickness of 2 mm and a size of 50 mm × 50 mm is prepared by a hot press quenching method, and left in an oven at 160 ° C. under air for 30 days.

Examples 1 to 14 After dry blending 2% by weight of a metal salt of benzenesulfonic acid or a metal salt of naphthalenesulfonic acid with the polycarbonate obtained in Synthesis Examples 1 and 2, a twin-screw extruder (Toshiba Machine Co., Ltd.) ), TM-35B, cylinder temperature 255 ° C, 2
Pellets were made using 00 rpm. Seat (2m
m thickness, UL test piece) was formed by a hot press quenching method. Transesterified aromatic polycarbonate resin mixed with metal benzenesulfonate or metal naphthalenesulfonate in the weight ratios shown in the table, a rubber-modified styrene resin (Sebian V: trade name, Daicel Chemical Industries, Ltd.) and acrylonitrile-styrene Resin (Sebian N: trademark: Daicel Chemical Industries, Ltd.) was mixed with a Henschel mixer, and then a twin-screw extruder (PCM-3 manufactured by Ikemi Tekko Co., Ltd.)
The mixture was melt-kneaded using (0) and pelletized. Using an injection molding machine (Meiyo SJ45 / 70, mold temperature 50 ° C),
Specimens for measuring physical properties (ASTM dumbbells) were prepared, and various physical properties were measured. The measurement results of various physical properties are shown in the table.

[0027]

[Table 1]

[Table 2] As is clear from the table, the resin composition of the present invention (Examples 1 to 3)
4, Examples 8 to 11) are other compositions (Examples 5 to 7, Example 12).
14) It is understood that the composition has excellent heat resistance and flame retardancy.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08L 55/02 C08L 55/02 (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 25/12 C08L 33/20 C08L 51 / 04 C08L 55/02 C08L 69/00

Claims (3)

(57) [Claims] 1. The method according to claim 1 , which is produced by a melt transesterification method .
One terminal hydroxyl group concentration of 10 to 90 wt% 3 mol% or more and less than 60 mol% der Ru aromatic polycarbonate and rubber-modified styrene resin and acrylonitrile - aromatic polycarbonate containing a mixture 90 to 10 wt.% Styrene copolymer A resin composition comprising substantially an aromatic phosphate ester
Contains no stells or fibrous reinforcements, and as a flame retardant
Among the compounds represented by the following general formula (I) or (II)
Aromatic polycarbonate containing one or more compounds selected from
Bonate resin composition . Embedded image (Wherein, X _{1 to} X ₆ : hydrogen or 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 an integer of 1 or 2. Note that X _{1 to} X ₆ , Y ₃ , Y ₄
May be in any of positions 1 to 8. ) 2. The aromatic polycarbonate is polymerized by using a nitrogen-containing basic compound or an alkali metal / alkaline earth metal compound as a catalyst, and contains boric acid or a borate ester and / or ammonium hydrogen phosphite. Aromatic polycarbonate resin composition. 3. A represented by reduction <br/> compound in one general formula (I) or (II) containing from 0.1 to 5 wt% claim 1 or claim 2
Serial mounting aromatic polycarbonate resin composition.