JPH08302178A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE: To obtain a polycarbonate resin composition excellent in transparency, impact resistance and heat resistance while having excellent flame retardancy. CONSTITUTION: 100 pts.wt. resin consisting of 1-99 pts.wt. aromatic polycarbonate resin (A) and 99-1 pts.wt. organopolysiloxane/polycarbonate copolymer (B) is mixed with 1-20 pts.wt. phosphoric ester compound (C) and 0-10 pts.wt. metal organosulfonate (D).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polycarbonate resin composition, and more specifically, it has excellent flame retardant properties.
The present invention also relates to a polycarbonate resin composition having excellent transparency, impact resistance and heat resistance.

[0002]

2. Description of the Related Art Polycarbonate resins have excellent mechanical and thermal properties, and are therefore widely used industrially including in the fields of automobiles, office automation equipment and electric and electronic fields. On the other hand, in recent years, mainly for applications such as office automation equipment and home electric appliances, there is a strong demand for flame retardant synthetic resin materials to be used, and in order to meet these demands, many flame retardants have been developed and studied. Usually, a halogen compound or the like is mainly used for making a polycarbonate resin flame-retardant, and in many cases, antimony trioxide or the like is also used as a flame-retardant aid. When a halogen compound is added to a synthetic resin as a flame retardant, the effect of flame retardancy is relatively large, but it may cause environmental pollution during a fire or incineration process, impairing the original mechanical properties of the polycarbonate resin. However, there are problems such as discoloration during molding, deterioration of physical properties due to long-term heat resistance, and large coloring. Therefore, it has been desired to reduce the amount of the halogen-based compound used in the flame-retardant resin.

A method of improving flame retardancy using an organic sulfonic acid metal salt is disclosed in JP-A-49-88943 and JP-A-50-9.
No. 8545, JP-A No. 50-98549, etc., but the effect of improving flame retardancy is insufficient. In addition, the composition in which the aromatic oligomer phosphate is mixed,
It is disclosed in JP-A-59-202240. However, in order to obtain excellent flame retardancy, it is necessary to add a large amount of aromatic oligomeric phosphoric acid ester, resulting in the drawback of impairing the original excellent mechanical and thermal properties of the polycarbonate resin. . Further, a method for improving impact resistance using an organopolysiloxane-polycarbonate copolymer is disclosed in JP-A-55-160052, JP-A-61-215652, JP-A-3-292359,
It is disclosed in Japanese Patent Laid-Open No. 4-285655. However, it has not been described that the organopolysiloxane-polycarbonate copolymer gives an effect of improving impact resistance in a polymer mixture containing an aromatic polycarbonate resin and a phosphate compound.

[0004]

SUMMARY OF THE INVENTION The present invention is intended to solve these problems of the prior art, and its object is to have excellent flame retardant properties and to have transparency, impact resistance and heat resistance. The object is to provide an excellent polycarbonate resin composition.

[0005]

Means for Solving the Problems The present inventor has made earnest studies as a result of obtaining a polycarbonate resin composition having excellent flame retardant properties and excellent transparency, impact resistance and heat resistance. By mixing a polycarbonate resin, an organopolysiloxane-polycarbonate copolymer and a phosphoric acid ester compound in a specific ratio,
The present invention has been completed by finding out that the above object can be achieved.

That is, the present invention relates to 100 parts by weight of a resin comprising (A) 1 to 99 parts by weight of an aromatic polycarbonate resin and (B) 99 to 1 parts by weight of an organopolysiloxane-polycarbonate copolymer, ) 1 to 20 parts by weight of a phosphoric acid ester compound and 0 to 10 parts by weight of (D) an organic sulfonic acid metal salt, the present invention relates to a polycarbonate resin composition.

The structure of the present invention will be described below. The (A) aromatic polycarbonate resin used in the present invention is produced by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method.

Representative examples of dihydric phenols are as follows:
2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3) , 5-Dimethylphenyl) propane, 2,2-bis (4-hydroxy-)
Examples thereof include 3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like. Of course, these dihydric phenols may be used alone or in admixture of two or more. Preferred dihydric phenols are bis (4-
Hydroxyphenyl) alkane type, especially bisphenol A or a mixture containing this as a main raw material. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate, and the like, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and a mixture thereof.

Further, a branching agent is used in combination with the above dihydric phenol in an amount of 0.01 to 3 mol%, particularly 0.1 to 1.0 mol%, to give a branched polycarbonate. You can also Specific branching agents include phloroglysin, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4,6-dimethyl-
2,4,6-tri (4-hydroxyphenyl) heptene-2,1,3,5-tri (2-hydroxyphenyl) benzole, 1,1,1, -tri (4-hydroxyphenyl) ethane, 2, 6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α, α ′, α ″
-A polyhydroxy compound exemplified by tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like, other 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol),
5-chlorisatin, 5,7-dichlorisatin, 5-
Bromisatin and the like are exemplified.

The viscosity average molecular weight of the aromatic polycarbonate resin is generally 10,000 to 100,000, preferably 15,000 to 60,000 in terms of molding or physical properties of a molded product. When producing a polycarbonate resin having these viscosity average molecular weights, an appropriate molecular weight modifier, a catalyst for accelerating the reaction, and the like can be added, if necessary. For example, as the monovalent aromatic hydroxy compound suitable for controlling the molecular weight, phenols substituted at the m-position or the p-position are common, and specifically, m-methylphenol,
p-methylphenol, m-propylphenol, p-
Alkyl-substituted compounds such as propylphenol, p-tert-butylphenol, p-long-chain alkyl-substituted phenol and halogen-substituted compounds such as p-bromophenol are preferred.

The organopolysiloxane-polycarbonate copolymer (B) used in the present invention is a copolymer having a polycarbonate block derived from diorganosiloxane and an aromatic polycarbonate block, and is known to those skilled in the art. Is well known. Preferable examples of this type of polycarbonate copolymer include the copolymers disclosed in JP-A-50-29695, JP-A-3-292359, and JP-A-4-202466. For example, a polycarbonate block derived from a diorganosiloxane composed of a structural unit represented by the following structural formula (1) and an aromatic polycarbonate block composed of a structural unit represented by the following structural formula (2): It is a block copolymer having both in the molecule.

[0012]

Embedded image

[0013]

Embedded image (In the structural formula (1), n represents an integer of 1 to 200, R represents an alkylene group having 2 to 6 carbon atoms, and B in the structural formula (2), B is a straight chain having 1 to 10 carbon atoms. A branched or cyclic alkylene group or alkylidene group, an aryl-substituted alkylene group, an arylene group, an -O- group, an -S- group,
It represents a —CO— group or a —SO ₂ — group, and R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. )

These polycarbonate copolymers can be produced by methods known to those skilled in the art, and such known methods include those described in the aforementioned patent specifications. That is, except that in the above method (A) for producing an aromatic polycarbonate resin, a part of the dihydric phenol is replaced with a silanized bisphenol that produces a structural unit represented by the structural formula (1). , Exactly the same method can be adopted. Further, this silanized bisphenol has an —O— group and an —OCO group bonded to benzene nuclei at both ends of the above structural formula (1).
A dihydric phenol in which all the groups are replaced with hydroxyl groups, and the bonding positions of the hydroxyl groups are o- and m- with respect to the -R- group.
Alternatively, it may be located at any position of p-.

The structural unit represented by the above structural formula (1) is
Although not particularly limited, in the organopolysiloxane-polycarbonate copolymer (B), preferably 0.2 to 5
A range of 0% by weight, particularly 0.5 to 25% by weight is suitable. The repeating number n of the siloxane unit in the structural formula (1) is in the range of 1 to 200, preferably 5 to 100.
Range. Examples of R in the structural formula (1) include groups such as ethylene, propylene, isopropylene, butylene, pentylene, and hexylene. The silanized bisphenol that produces the structural unit represented by the structural formula (1) is obtained by polymerizing a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol or isopropenylphenol, by predetermined polymerization. It is easily produced by subjecting the end of the polysiloxane chain having a degree (n) to a hydrosilation reaction.

In the present invention, (A) the aromatic polycarbonate and (B) the organopolysiloxane-polycarbonate copolymer are in a weight ratio of (A) :( B) = 1: 99-.
Selected from the range of 99: 1. In addition, these resins (A)
It is preferable to select a blending composition in which the amount of the organopolysiloxane is 1 to 25 parts by weight with respect to the total of 100 parts by weight of the + (B) component. When the amount of the organopolysiloxane is less than 1 part by weight, the effect of improving impact resistance is insufficient, while when it is more than 25 parts by weight, the transparency is lowered, which is not preferable.

Examples of the phosphoric acid ester compound (C) used in the present invention include, but are not limited to, phosphoric acid ester compounds represented by the following structural formula (3).

[0018]

Embedded image (In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an organic group, X represents a divalent or higher valent organic group, p is 0 or 1, and q is is an integer of 1 or more, r is an integer of 0 or more. However, if r is 0, R ^5, at least one of R ⁶ and R ^8, and if r is an integer other than 0, At least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ represents an organic group.)

In the structural formula (3), organic groups R ^{5 to} R
Examples of ⁸ include an optionally substituted alkyl group, a cycloalkyl group, an aryl group and the like. When substituted, examples of the substituent include an alkyl group,
Examples thereof include an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group and a halogenated aryl group. Furthermore, a group in which these substituents are combined, such as an arylalkoxyalkyl group, or these substituents, an oxygen atom, a sulfur atom,
A group bonded by a nitrogen atom or the like and combined, for example, an arylsulfonylaryl group may be used as a substituent.

In the structural formula (3), the divalent or higher valent organic group X is formed by removing one or more hydrogen atoms bonded to carbon atoms from the above-mentioned organic groups R ^{5 to} R ^8. Two
It means a group having a valency or higher. Examples thereof include alkylene groups, optionally substituted phenylene groups, polynuclear phenols, for example, polyvalent residues derived from bisphenols. Particularly preferred are divalent or higher-valent residues derived from hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p'-dihydroxydiphenylsulfone, dihydroxynaphthalene and the like. Of course, in these residues, the relative positions of two or more free valences are arbitrary.

Specific examples of the phosphoric acid ester compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate when r is 0 in the above structural formula (3). , Tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-)
Examples include dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) and bis (chloropropyl) monooctyl phosphate. When r is an integer other than 0 in the structural formula (3), bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene triphosphate, etc., in which p is 1 can be mentioned. Preferred are triphenyl phosphate and various bisphosphates. These compounds may be used alone or in combination of two or more.

These phosphoric acid ester compounds are usually used in an amount of 1 to 100 parts by weight of the resin (A) + (B) in total.
20 parts by weight, preferably 5 to 15 parts by weight are mixed. When it is less than 1 part by weight, the effect of improving flame retardancy is insufficient, while when it is more than 20 parts by weight,
It is not preferable because impact resistance and heat resistance are significantly reduced.

The organic sulfonic acid metal salt (D) used in the present invention is preferably an alkali metal salt or an alkaline earth metal salt, particularly a sodium salt or a potassium salt.
Specifically, sodium 3,4-dichlorobenzenesulfonate, sodium 2,4,5-trichlorobenzenesulfonate, sodium benzenesulfonate, disodium naphthalene-2,6-disulfonate, sodium p-iodobenzenesulfonate. , 4,4'-dibromodiphenyl-3-sodium sulfonate, 2,3,4,5,6
-Sodium pentachloro-β-styrenesulfonate,
Sodium 4,4'-dichlorodiphenyl sulfide-3-sulfonate, disodium tetrachlorodiphenyl ether disulfonate, disodium 4,4'-dichlorobenzophenone-3,3'-disulfonate, 2,5-
Sodium dichlorothiophene-3-sulfonate, potassium diphenylsulfone-3-sulfonate, 2,4,6
-Sodium salt of dimethyl trichloro-5-sulfoisophthalate, Potassium salt of sulfonic acid of dichlorophenyl 2,4,5-trichlorobenzenesulfonate, 4'-
[1,4,5,6,7,7'-hexachlorobicyclo-
Examples include [2,2,1] -hept-5-en-endo-yl] benzenesulfonate and potassium perfluorobutanesulfonate. Particularly preferably 3,4
-Sodium dichlorobenzenesulfonate, 2,4,5
-Sodium trichlorobenzenesulfonate, sodium benzenesulfonate, potassium diphenylsulfone-3-sulfonate, potassium perfluorobutanesulfonate. These metal salts may be used alone or 2
You may use it in combination of 2 or more types. These organic sulfonic acid metal salts are used in an amount of 0 to 10 parts by weight, preferably 0 to 2 parts by weight, based on 100 parts by weight of the resin (A) + (B) in total. When the amount of the sulfonate is more than 10 parts by weight, the thermal stability is impaired, which is not preferable.

The resin composition of the present invention can be produced by mixing the above components with a mixer such as a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll and an extruder. In the production of the composition of the present invention, the method of mixing the components and the order of mixing are not particularly limited. The most preferable method is a method in which all the components are mixed in advance with a tumbler, a V-type blender or the like and uniformly melt-mixed by an extruder. However, depending on the shape of the components, a mixture of two or more of these components Alternatively, a method of mixing the remaining components may be used.

Further, in the resin composition of the present invention, various additives such as stabilizers, mold release agents, ultraviolet absorbers, dyes and pigments are added in an amount in which the effects of the present invention are manifested within a range that does not impair the effects of the present invention. It does not matter even if an inorganic filler is included. The flame-retardant resin composition thus obtained can be easily molded by a method such as extrusion molding, injection molding, compression molding,
Further, it can be applied to blow molding, vacuum molding, gas injection molding and the like, and can be suitably used as a material for various electronic parts such as electronic and electric products requiring excellent flame retardancy, housings or chassis for OA equipment and various parts.

[0026]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples without departing from the gist of the invention. All parts in the following examples represent parts by weight. The physical properties are evaluated by drying the resin composition pellets of Examples or Comparative Examples at 120 ° C. for 6 hours and then using an injection molding machine (manufactured by Japan Steel Works, Ltd., trade name J-50EP) to measure the cylinder temperature. Two
A designated test piece was molded at 70 ° C. and a mold temperature of 80 ° C., and the procedure was as follows.

1) Transparency Regarding the transparency, a molded product having a thickness of 1/16 "was visually observed. The evaluation was based on the following criteria.
X indicates a defect. 2) Izod Impact Strength A 1/8 "notched impact test of ASTM D-256 was carried out using an impact test piece prepared according to ASTM standard D-256. The Izod impact strength was kg.cm/
Display in units of cm. 3) Heat distortion temperature The heat distortion temperature was measured at a load of 18.5 kg using a test piece prepared according to ASTM standard D-648.
The test of TM D-648 was carried out. Heat distortion temperature is ℃
Display in units of. 4) Using the A-1 No. combustion test piece prepared according to LOI JIS standard K7201, the combustion test of JIS K7201 (LO
I) was carried out.

In the examples below, the terms and abbreviations used have the following meanings. (Terms or abbreviations) (Meaning) (A) PC aromatic polycarbonate resin, manufactured by Mitsubishi Gas Chemical Co., Inc., trade name Iupilon E-2000, viscosity average molecular weight 29,000. (B) SiPC15 Organopolysiloxane-Polycarbonate Copolymer A copolymer in which the amount of polydimethylsiloxane is about 15% by weight of the total copolymer, and the viscosity average molecular weight is 29,000. (B ') SiPC05 Organopolysiloxane-polycarbonate copolymer A copolymer in which the amount of polydimethylsiloxane is about 5% by weight of the whole copolymer, and the viscosity average molecular weight is 29,000. (C) P X condensed phosphoric acid ester, manufactured by Daihachi Chemical Co., Ltd. The structural formula is as follows.

[Chemical 4] (C ') TPP Triphenyl phosphate, manufactured by Daihachi Chemical Co., Ltd., trade name TPP. (D) KSS Potassium diphenylsulfone-3-sulfonate, manufactured by SEAL SANDS CHEMICAL, trade name KSS. (E) ABS ABS resin, product name UX050 manufactured by Ube Cycon Co., Ltd. (E ') SAN SAN resin, manufactured by Ube Saikon Co., Ltd., product name SR30B.

Examples 1 to 4 and Comparative Examples 1 to 4 The components shown in Table 1 (Examples) or Table 2 (Comparative Examples) were used.
After mixing in the mixing ratios shown in the table, a 40 mmφ single screw extruder (manufactured by Isuzu Machinery Co., Ltd.) was used and extruded at a cylinder temperature of 270 ° C. to form pellets. The composition and evaluation results of physical properties are shown in Tables 1 and 2.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

According to the present invention, excellent flame retardant properties are provided,
A polycarbonate resin composition having excellent transparency, impact resistance and heat resistance can be provided. Therefore, the resin composition of the present invention is industrially very useful.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08L 83/10 LRY C08L 83/10 LRY

Claims (3)

[Claims] 1. To 100 parts by weight of a resin composed of 1 to 99 parts by weight of an aromatic polycarbonate resin (A) and 99 to 1 parts by weight of an organopolysiloxane-polycarbonate copolymer (B), (C) a phosphoric ester A polycarbonate resin composition comprising 1 to 20 parts by weight of a compound and 0 to 10 parts by weight of (D) an organic sulfonic acid metal salt. 2. The polycarbonate resin composition according to claim 1, wherein the organopolysiloxane-polycarbonate copolymer (B) has two structural units represented by the following structural formulas (1) and (2). Embedded image Embedded image (In the structural formula (1), n represents an integer of 1 to 200, R represents an alkylene group having 2 to 6 carbon atoms, and B in the structural formula (2), B is a straight chain having 1 to 10 carbon atoms. A branched or cyclic alkylene group or alkylidene group, an aryl-substituted alkylene group, an arylene group, an -O- group, an -S- group,
It represents a —CO— group or a —SO ₂ — group, and R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. ) 3. The polycarbonate resin composition according to claim 1 or 2, wherein the phosphoric acid ester compound (C) is represented by the following structural formula (3). Embedded image (In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an organic group, X represents a divalent or higher valent organic group, p is 0 or 1, and q is is an integer of 1 or more, r is an integer of 0 or more. However, if r is 0, R ^5, at least one of R ⁶ and R ^8, and if r is an integer other than 0, At least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ represents an organic group.)