JP2003147219A - Flame-retardant organic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aromatic ring-containing organic resin composition having excellent formability and flame retardancy. SOLUTION: This flame-retardant resin composition is characterized by comprising (A) 100 pts.wt. of an aromatic ring-containing organic resin, (B) 0.01 to 4 pts.wt. of an epoxy group-containing organopolysiloxane, and (C) 0.01 to 20 pts.wt. of an aryl group-containing branched organopolysiloxane represented by an average molecular formula: (R<1> 3 SiO1/2 )a (R<2> 2 SiO2/2 )b (R<3> SiO3/2 )c (SiO4/2 )d (R<4> O1/2 )e (HO1/2 )f .

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant organic resin composition comprising an aromatic ring-containing organic resin, an epoxy group-containing organopolysiloxane and a branched organopolysiloxane.

[0002]

2. Description of the Related Art Aromatic ring-containing organic resins represented by aromatic polycarbonate resins are excellent in mechanical strength, electrical characteristics, etc., so that they can be used in office automation equipment, electric / electronic equipment, automobiles, construction / civil engineering, etc. Used in the field. Conventionally, as a method for making such an aromatic ring-containing organic resin flame-retardant, a method of mixing a compound containing a chlorine atom or a bromine atom into these organic resins has been adopted. However, the organic resin composition containing this kind of compound has a drawback that a large amount of black smoke is generated at the time of combustion, or a gas harmful to the human body or a gas corroding a metal or the like is generated.

Therefore, many flame-retardant polycarbonate resin compositions which do not generate harmful gas to human body have been proposed. For example, JP-A-8-176425 discloses an epoxy group-containing silicone resin (polyglycidoxypropylsilsesquioxane obtained by hydrolyzing γ-glycidoxypropyltrimethoxysilane) and an organic alkali metal salt. An aromatic polycarbonate resin composition prepared by blending has been proposed. However, since this composition has a large amount of epoxy groups contained in the epoxy group-containing polyorganosiloxane, it may have poor compounding stability in an aromatic polycarbonate resin composition, and its moldability may deteriorate. There was a problem. Further, in JP-A-10-139964, an aromatic polycarbonate resin is composed of a bifunctional siloxane unit (D unit) and a trifunctional siloxane unit (T unit) and has a high molecular weight of more than 10,000. A polycarbonate composition containing a silicone resin has been proposed. However, this composition has problems in that it has poor moldability and insufficient flame retardancy.
Further, there is a problem that it is not easy to manufacture this product.

Further, JP-A No. 11-140294 proposes a flame-retardant polycarbonate resin composition in which an aromatic polycarbonate resin is mixed with a silicone resin containing 80 mol% or more of phenyl groups. Japanese Unexamined Patent Publication (Kokai) No. 11-222559 proposes a flame-retardant aromatic polycarbonate resin composition containing a silicone resin containing a phenyl group and an alkoxy group. However, this composition cannot be said to have sufficient flame retardancy and was not satisfactory depending on the application. Furthermore, JP-A-11
No. 140329 discloses a flame-retardant aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin, a silicone resin containing a phenyl group and an alkoxy group, and silica powder. However, this resin composition has a problem that it is necessary to add silica powder and the manufacturing process is complicated.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that an aromatic ring-containing organic resin such as an aromatic polycarbonate resin is specified as an epoxy group-containing organopolysiloxane. The inventors have found that the flame retardancy is remarkably improved by blending a branched organopolysiloxane and have reached the present invention. That is, an object of the present invention is to provide an aromatic ring-containing organic resin composition having excellent moldability and flame retardancy.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises (A) an aromatic ring-containing group.
Machine resin (100 parts by weight), (B) epoxy group-containing ogre
Nopolysiloxane (0.01 to 4 parts by weight), (C) average
Molecular formula: (R¹ ₃SiO_1/2)_a(R² ₂SiO_2/2)_b(R³Si
O_3/2)_c(SiO_4/2)_d(R^Four O_1/2)_e(HO_1/2)_f(formula
Medium, R¹, R², R³Is alkyl having 1 to 12 carbon atoms
Group, alkenyl group having 2 to 12 carbon atoms and carbon atom
Monovalent coal selected from the group consisting of allyl groups of 6 to 12
A hydrogenated group, R³Content of aryl group of 20 to 1
It is in the range of 00 mol%. R^FourIs an alkyl group.
a, b, d, e, f are 0 or a positive number, and c is a positive number
Is. ) Branched organopolysiloxane
(0.01 to 20 parts by weight),
It relates to a flame-retardant organic resin composition.

To explain this, the component (A) may be any organic resin containing an aromatic ring, and its type is not particularly limited. Such aromatic ring-containing organic resins include aromatic polycarbonate resins and alloys thereof; polyphenylene ether resins and alloys thereof; polysulfone resins; polyarylate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, etc. Aromatic polyester resin; aromatic polyamide resin; polyimide resin; polyamideimide resin; polyphenylene sulfide resin; polystyrene resin, high impact polystyrene resin, A
Examples thereof include thermoplastic organic resins such as styrene resins such as BS resins and AS resins; epoxy resins such as novolac type epoxy resins and biphenyl type epoxy resins; and thermosetting resins such as phenol resins. Of these, aromatic polycarbonate resins and alloys thereof are particularly preferably used.

The epoxy group-containing organopolysiloxane of the component (B) is a component which is a feature of the present invention, and when used in combination with the component (C) described later, it serves to improve the flame retardancy of the composition of the present invention. . The component (B) may be any organopolysiloxane containing an epoxy group in the molecule, and the type thereof is not particularly limited. This epoxy group is usually bonded to the silicon atom via a divalent organic group. That is, it is bonded to a silicon atom as an epoxy group-containing organic group. Examples of the epoxy group-containing organic group include a 2,3-epoxypropyl group, a 3,4-epoxybutyl group, a 4,5-epoxypentyl group, a 2-glycidoxyethyl group, and a 3-glycidoxypropyl group. , 4-glycidoxybutyl group, 2- (3,4-epoxycyclohexyl) ethyl group, and 3- (3,4-epoxycyclohexyl) propyl group. Examples of the silicon atom-bonded organic group other than the epoxy group-containing organic group bonded to the silicon atom include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a vinyl group, an allyl group. , Alkenyl groups such as butenyl group, pentenyl group, hexenyl group; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl groups such as benzyl group, phenethyl group; chloromethyl group, 3-chloropropyl group, Examples thereof include halogen atom-substituted alkyl groups such as 3,3,3-trifluoropropyl group and nonafluorobutylethyl group. The molecular structure thereof may be linear, branched, network, or cyclic, and linear organopolysiloxane is preferable. The weight average molecular weight of the component (B) is preferably 100 to 100,000,
More preferably, it is 300 to 20,000. Representative examples of such epoxy group-containing organopolysiloxanes include compounds represented by the following general formulas 1 and 2. In the following formula, l, m, and n are positive numbers.

[0009]

Embedded image General formula 1:

[0010]

Embedded image General formula 2: Here, the content of the epoxy group in the component (B) is preferably 0.01 to 60 mol% and more preferably 0.1 to 15 mol% with respect to the total silicon atom-bonded organic groups. preferable. This is because if the content of epoxy groups in the component (B) is less than 0.01 mol% with respect to all the silicon atom-bonded organic groups, the flame retardancy decreases, and if it exceeds 60 mol%, it is difficult. This is because not only the flammability is lowered, but also the flowability of the obtained organic resin composition is lowered and the moldability is lowered. The blending amount of this component is 0.01 to 4 parts by weight with respect to 100 parts by weight of the component (A).

Component (C) is a feature of the present invention.
When used in combination with the above component (B), the composition of the present invention
It has the function of improving the flame retardancy of products. Such (C) success
Minute is the average molecular formula: (R¹ ₃SiO_1/2)_a(R² ₂SiO_2/2)_b(R³Si
O_3/2)_c(SiO_4/2)_d(R^Four O_1/2)_e(HO_1/2)_f(formula
Medium, R¹, R², R³Is alkyl having 1 to 12 carbon atoms
Group, alkenyl group having 2 to 12 carbon atoms, 6 carbon atoms
To 12 monovalent hydrocarbons selected from the group consisting of aryl groups
R is a base³Content of aryl groups of 20-100
Mol%. R^FourIs an alkyl group. a, b, d,
e and f are 0 or a positive number, and c is a positive number. )so
It is a branched organopolysiloxane shown. (C)
As described above, the component is R in one molecule.³SiO_3/2Indicated by
Has a trifunctional siloxane unit (T unit)
Depending on the formula: R¹ ₃SiO_1/2Monofunctional Shiroki represented by
Sun unit (M unit) and formula: R² ₂SiO_2/2Indicated by 2
It has a functional siloxane unit (D unit)
In addition to these siloxane units, the formula: SiO_4/2
Containing a tetrafunctional siloxane unit (Q unit) represented by
It does not matter as long as the object of the present invention is not impaired.

The component (C) has an average molecular formula: (R² ₂SiO_2/2)_b(R³SiO_3/2)_c(SiO_4/2)_d(R^FourO
_1/2)_e(HO_1/2)_f (In the formula, R², R³, R^Four, B, c, d, e, f are the above
Is the same as. ), Average molecular formula: (R² ₂SiO_2/2)_b(R³SiO_3/2)_c(HO_1/2)_f (In the formula, R², R³, B, c, f are the same as above.
It ) Or the average molecular formula: (R³SiO_3/2)_c(HO_1/2)_f (In the formula, R³, C, f are the same as above. )
Is preferably a branched organopolysiloxane
Yes.

In the above formula, specific examples of R ¹ , R ² and R ³ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group; vinyl group, allyl group. Groups, butenyl groups, pentenyl groups, hexenyl groups, and other alkenyl groups; phenyl groups, tolyl groups, xylyl groups, naphthyl groups, and other aryl groups. Of these, R ³ is required to have an aryl group content within the range of 20 to 100 mol%, preferably within the range of 50 to 100 mol%, and within the range of 70 to 100 mol%. It is more preferable that there is. Moreover, a phenyl group is preferable as the aryl group R ^3, it is preferred if R ³ is a phenyl group which phenyl group content is within the range of 70 to 100 mol%. The amount of phenyl groups in all the substituents is not particularly limited, but is preferably 20 to 100 mol%, more preferably 50 to 100 mol%. When the composition of the present invention is required to have transparency, the content of phenyl groups in all the substituents is preferably 90 mol% or more.

A hydroxyl group bonded to a silicon atom may be present in the component (C). In this case, the hydroxyl group content is 0 to
It is preferably 7% by weight. Further, in the component (C), a silicon atom-bonded methoxy group, ethoxy group, n
An alkoxy group having 1 to 12 carbon atoms, which is exemplified by a propoxy group, an isopropoxy group, a butoxy group and the like, may be present. The component (C) has a weight average molecular weight of 3
It is preferably from 00 to 10,000. When the weight average molecular weight exceeds 10,000, problems such as deterioration of moldability of the composition of the present invention may occur. In addition, it is often difficult to synthesize them. This weight average molecular weight is usually determined by gel permeation chromatography (GP
Quantified by C).

More specifically, the component (C) is an average molecule.
formula: ((CH₃)₂SiO_2/2)_b(C₆H_FiveSiO_3/2)_c(HO_1/2)_f (In the formula, b, c, and f are the same as above.) Yes
Is the average molecular formula: (R³SiO_3/2)_c(HO_1/2)_f (In the formula, R³Is a propyl group or a phenyl group
, C and f are the same as above. ) Branched
It is preferably an organopolysiloxane.

The blending amount of this component is 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight, and more preferably 0.1 to 1 part by weight, relative to 100 parts by weight of the component (A).
0 parts by weight. This is because if the blending amount is less than 0.01 part by weight, the mechanical strength of the molded product of the composition of the present invention will be reduced.

The composition of the present invention comprises the above-mentioned component (A), component (B) and component (C). In order to further enhance flame retardancy, in addition to these components, organic acid (D) is added. Alternatively, an alkali metal salt of an organic acid ester or an alkaline earth metal salt of an organic acid or an organic acid ester can be blended. Examples of the organic acid that constitutes the component (D) include organic sulfonic acids and organic carboxylic acids, and examples of the organic acid ester include organic phosphoric acid esters. Examples of the alkali metal include sodium, potassium, lithium and cesium, and examples of the alkaline earth metal include magnesium, calcium, strontium and barium. Among these, metal salts of organic sulfonic acids are preferably used, and further metal salts of perfluoroalkanesulfonic acid and metal salts of aromatic sulfonesulfonic acid are preferably used. Specific examples of the metal salt of perfluoroalkanesulfonic acid include sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, sodium perfluoromethylbutanesulfonate,
Perfluoromethylbutane-potassium sulfonate, per
Examples thereof include sodium fluorooctane-sulfonate and potassium perfluorooctane-sulfonate. Specific examples of the aromatic sulfonesulfonic acid metal salt include sodium salt of diphenylsulfone-3-sulfonic acid, potassium salt of diphenylsulfone-3-sulfonic acid, 4,4
-Dibromodiphenyl-sulfone-3-sulfonic acid sodium salt, 4,4-dibromodiphenyl-sulfone-
Potassium salt of 3-sulfonic acid, calcium salt of 4-chloro-4-nitrodiphenylsulfone-3-sulfonic acid,
Examples thereof include disodium salt of diphenyl sulfone-3,3-disulfonic acid and dipotassium salt of diphenyl sulfone-3,3-disulfonic acid. The blending amount of this component is 0.02 to 1% by weight based on 100 parts by weight of the component (A).

The composition of the present invention comprises the above-mentioned components (A) to (C) or (A) to (D), and in order to further improve the flame retardancy, it further comprises (E) a fluororesin. Powders can be included. Examples of the fluororesin constituting the fluororesin powder include a fluoroethylene resin (a polymer of a monomer in which a hydrogen atom of ethylene is replaced by one or more fluorine atoms, a representative example, a tetrafluoroethylene resin powder), Examples thereof include trifluorochloroethylene resin, tetrafluoroethylene hexafluoroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, and difluorodichloroethylene resin. The shape of these fluororesin powders is generally spherical, but may be fibrous. The blending amount of this component is usually 0.01 to 100 parts by weight of the component (A).
5 parts by weight.

The composition of the present invention may contain various additives known to be added to an aromatic ring-containing organic resin, as long as the object of the present invention is not impaired. Examples of such additives include glass fiber and glass beads.
Glass, glass flakes, carbon black, calcium sulfate, calcium carbonate, calcium silicate, titanium oxide,
Inorganic fillers such as alumina, silica, asbestos, talc, clay, mica, and quartz powder; organic resin additives such as various synthetic resins and various elastomers; hindered phenol antioxidants, phosphite ester additives Antioxidants such as antioxidants, phosphate-based antioxidants, amine-based antioxidants; lubricants such as aliphatic carboxylic acid esters, paraffins and polyethylene waxes; various organic or inorganic pigments and colorants; benzotriazo -Ultraviolet absorbers, benzophenone-based ultraviolet absorbers and other ultraviolet absorbers; hindered amine-based light stabilizers and other light stabilizers; phosphorus-based flame retardants and other flame retardants; various release agents; various electrification agents An inhibitor is exemplified.

The composition of the present invention comprises the above components (A) to (C).
It is easily produced by uniformly mixing the components, or the components (A) to (D) or the components (A) to (E). Examples of the apparatus for producing the composition of the present invention include a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, and a single screw.
Examples of the extruder include a twin screw extruder, a twin screw extruder, a kneader, and a multi-screw extruder. Here, it is preferable to mix the above components under heating at 200 to 350 ° C.

Since the composition of the present invention as described above is excellent in moldability and flame retardancy, it is suitable for use as a housing material for household electric appliances, automobile interiors, etc., an electric / electronic component material, etc. by utilizing such characteristics. It

[0022]

EXAMPLES Next, the present invention will be described in detail with reference to Examples and Reference Examples. In the examples, the flame retardancy of the aromatic polycarbonate resin composition was measured by the oxygen index according to JIS-K7201 "Plastic combustion test method by oxygen index method". The moldability was evaluated by measuring the melt index (MI value) according to JIS-K7210. This measurement is 300 with a load of 1.2 kg.
Performed at ° C. Further, the epoxy group-containing organopolysiloxanes (SNR1, SNR2 and SNR6) synthesized in Reference Examples 1, 2 and 6 and the branched organopolysiloxane (SNR synthesized in Reference Examples 3 to 5) (SNR).
3, SNR4 and SNR5) had the average molecular formulas shown in Table 1 and the properties shown in Table 2. In addition, Table 1
In, R represents a γ-glycidoxypropyl group, and M
e represents a methyl group, Pr represents a propyl group, and Ph represents a phenyl group. n is the number whose weight average molecular weight is the value shown in Table 2. The analysis of the chemical structure of the branched organopolysiloxane used in the examples was carried out by using nuclear magnetic resonance spectrum (NMR), and the weight average molecular weight was measured by gel permeation chromatography.
(GPC). This weight average molecular weight is a value converted into standard polystyrene having a known molecular weight.

[0023]

[Reference Example 1] Production of epoxy group-containing organopolysiloxane (SNR1) A stirring device, a cooling device, a dropping funnel, and a thermometer were attached.
In a 1 L four-necked flask, 300 g of dimethylpolysiloxane having a silicon atom-bonded hydrogen atom at both ends (dimethylsiloxane unit 60), 150 g of toluene and 16 g of allyl glycidyl ether were placed. A catalytic amount of chloroplatinic acid in isopropanol was added dropwise thereto. Further, a saturated aqueous solution of sodium bicarbonate sufficient to neutralize the acid was added. Then, the mixture was heated and stirred to cause a reaction. After the reaction was completed, the solvent was distilled off and the insoluble matter was filtered to obtain an epoxy group-containing organopolysiloxane. As a result of analysis, the epoxy group-containing organopolysiloxane had an average structural formula shown below. The weight average molecular weight was 4,600 and the epoxy equivalent was 2,300.

[Chemical 3]

[0024]

[Reference Example 2] Production of epoxy group-containing organopolysiloxane (SNR2) A stirring device, a cooling device, a dropping funnel, and a thermometer were attached.
In a 1 L four-necked flask, 200 g of dimethylsiloxane / methylhydrogensiloxane copolymer (dimethylsiloxane unit 120, methylhydrogensiloxane unit 174) with trimethylsiloxy groups blocked at both ends, 100 g of toluene, and 205 g of allyl glycidyl ether.
I put it in. A catalytic amount of chloroplatinic acid in isopropanol was added dropwise thereto. Furthermore, a saturated aqueous solution of sodium bicarbonate sufficient to neutralize the acid was added. Then, the mixture was heated and stirred to cause a reaction. After completion of the reaction, the solvent was distilled off and the insoluble material was filtered to obtain an epoxy group-containing organopolysiloxane. As a result of analysis, the epoxy group-containing organopolysiloxane had an average structural formula shown below. The weight average molecular weight was 39000 and the epoxy equivalent was 230.

[0025]

[Chemical 4]

[0026]

[Reference Example 3] Branched organopolysiloxane (SNR3)
The toluene (180 g), isopropyl alcohol (60 g), and water (250 g) were put into a 2 L four-necked flask equipped with a stirrer, a cooling device, a dropping funnel, and a thermometer.
Phenyltrichlorosilane (147
A mixed solution of g) and isopropyltrichlorosilane (52.8 g) was added dropwise. After the dropwise addition was completed, the mixture was stirred at room temperature for 30 minutes and then refluxed for 3 hours in order to allow hydrolysis to proceed completely.
Then, it left still and the water layer was removed. Subsequently, water was added, and the mixture was stirred and left standing to remove the aqueous layer, and the washing operation was repeated until the washing liquid became neutral. Water was removed from the obtained toluene solution by azeotropic dehydration. After cooling, the insoluble matter was removed by filtration, and toluene and the like were removed by distillation under reduced pressure to obtain 115.2 g of a solid branched organopolysiloxane. Obtained branched organopolysiloxane (hereinafter, SNR3)
Is 70 mol% of PhSiO _3/2 unit and C ₃ H ₇ SiO _3/2
Containing 30 mol% of units and 6.0 wt% of hydroxyl groups,
Its weight average molecular weight was 1,600.

[0027]

[Reference Example 4] Branched organopolysiloxane (SNR4)
The toluene (110 g), methyl ethyl ketone (40 g), and water (40 g) were placed in a 1 L four-necked flask equipped with a stirrer, a cooling device, a dropping funnel, and a thermometer. Then, while cooling the flask in an ice bath, phenyltrichlorosilane (114.8 g), dimethyldichlorosilane (17.5 g), toluene (40
The mixed solution of g) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 30 minutes, and then refluxed for 1 hour in order to allow hydrolysis to proceed completely. After cooling, 30 ml of toluene was added and the mixture was allowed to stand and the aqueous layer was removed. Subsequently, water was added, and the mixture was stirred and left to stand to remove the aqueous layer, and the washing operation was repeated three times. Further, aqueous sodium hydrogen carbonate (4% by weight aqueous solution of sodium bicarbonate) was added to the toluene phase, the mixture was refluxed for 1 hour, cooled, and washed 3 times with water to obtain a toluene solution of a branched organopolysiloxane. The solid content of the toluene solution of this branched organopolysiloxane was adjusted to 30% by weight, and 0.8 g of a 10% aqueous solution of potassium hydroxide was added thereto.
Then, an ester adapter was attached and the generated water was separated and refluxed. Cool for 4 hours after the start of reflux,
After neutralization with acetic acid, the solid was washed with water three times, dried and solidified to obtain solid organopolysiloxane. The obtained organopolysiloxane (hereinafter referred to as SNR4) contained 80 mol% of PhSiO _3/2 units and 20 mol% of Me2SiO _2/2 units, and contained 3.4 wt% of hydroxyl groups at the molecular chain terminals. The weight average molecular weight was 4000.

[0028]

[Reference Example 5] Branched organopolysiloxane (SNR5)
In a 1 L 4-neck flask equipped with a stirrer, cooling device, dropping funnel, and thermometer, 90 g of toluene and 430 g of water
Was charged, and after heating to 80 ° C., a mixed solution of phenyltrichlorosilane (169 g) and dimethyldichlorosilane (26 g) was added dropwise. Then, the mixture was refluxed for 1 hour in order to allow the hydrolysis to proceed completely. After cooling, the mixture was allowed to stand to remove the water layer, and subsequently water was added and stirred, and the mixture was left to stand to remove the water layer, and the water washing operation was repeated three times. Next, an ester adapter was attached, and the generated water was separated and refluxed for 1 hour, and then cooled to room temperature. The obtained organopolysiloxane solution was filtered to remove insoluble materials, and dried and solidified to obtain solid organopolysiloxane. The obtained organopolysiloxane (hereinafter, SNR5) contained 80 mol% of PhSiO _3/2 units and 20 mol% of Me ₂ SiO _2/2 units, and contained 1.7 wt% of hydroxyl groups at the molecular chain ends. It was The weight average molecular weight was 20,000.

[0029]

[Reference Example 6] Production of epoxy group-containing organopolysiloxane (SNR6) 50 equipped with a stirrer, a cooling device, a dropping funnel, and a thermometer
In a 0 ml four-necked flask, 3-glycidoxypropyltrimethoxysilane (50 g) and methanol (100 g) were added.
g) was added. Then, 0.1N hydrochloric acid (23 g) was added dropwise from the dropping funnel while stirring. The mixture was stirred as it was at room temperature for 30 minutes and then at 70 ° C. for 2 hours. Then, it was distilled under reduced pressure to obtain 35 g (hereinafter, SNR6) of colorless and transparent poly (3-glycidoxypropyl) silsesquioxane (viscous liquid). The viscosity of this product is 1500 mPa
-S, and the weight average molecular weight was 600.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

Examples 1 to 7: As the aromatic ring-containing organic resin (A), an aromatic polycarbonate resin (manufactured by Idemitsu Petrochemical Co., Ltd .; trade name, Tufflon A1900) was used.
As the epoxy group-containing organopolysiloxane of the component (B), SNR1 and SNR2 shown in Tables 1 and 2 above are used, and as the branched organopolysiloxane of the component (C), SNR3 to SNR3 shown in the above Tables 1 to 2 are used. Using SNR5,
Using sodium trichlorobenzenesulfonate as the component (D) and using perfluoroethylene powder (manufactured by Daikin Industries, Ltd .; trade name, polyflon MPA, FA-500) as the component (E), these components will be described later. The flame-retardant polycarbonate resin composition was manufactured by mixing at the mixing ratios shown in Table 3 and Table 4. The manufacturing method was as follows. Mixing device for aromatic polycarbonate resin (Toyo Seiki Seisakusho Co., Ltd., Labo Plastomill)
And heated under the conditions of 280 to 320 ° C. to melt. Then, branched organopolysiloxane was added and kneaded. In Example 5, fluororesin powder was further added and kneaded. In Example 6 and Example 7, sodium trichlorobenzene sulfonate was further added and kneaded. The moldability {melt index (MI value)} of the obtained flame-retardant polycarbonate resin composition was measured. Next, this composition was injection molded at a molding temperature of 280 to 320 ° C. The oxygen index and transparency of the obtained molded product were measured.
The results of these measurements are shown in Tables 3 and 4 below.

[0033]

Comparative Examples 1 to 8 Polycarbonate resin compositions were produced in the same manner as in Example 1 except that neither the epoxy group-containing organopolysiloxane nor the branched organopolysiloxane was blended. The moldability (MI value) of these compositions was measured. Next, this composition was injection molded at a molding temperature of 280 to 320 ° C. The oxygen index and transparency of the obtained molded product were measured. The results of these measurements are shown in Table 5 below.

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

[0037]

The organic resin composition of the present invention comprises (A) component, (B) component and (C) component, and in particular of (B) component epoxy group-containing organopolysiloxane and (C) component. Since it contains a branched organopolysiloxane,
It is characterized by excellent moldability and flame retardancy.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Haruhiko Furukawa             2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow             Corning Silicon Co., Ltd. R & D             In headquarters (72) Inventor Koji Shiromoto             2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow             Corning Silicon Co., Ltd. R & D             In headquarters (72) Inventor Hiroshi Ueki             2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow             Corning Silicon Co., Ltd. R & D             In headquarters (72) Inventor Koji Morita             2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow             Corning Silicon Co., Ltd. R & D             In headquarters F term (reference) 4J002 BC021 BD124 BN121 BN151                       CC031 CD041 CF061 CF071                       CF161 CG001 CH071 CL001                       CM041 CN031 CP033 CP052                       CP063 EG026 EG036 FD136

Claims (9)

[Claims] 1. A (A) an aromatic ring-containing organic resin (100 parts by weight), (B) an epoxy group-containing organopolysiloxane (0.01 to 4 parts by weight), (C) the average molecular formula: (R ¹ ₃ SiO _1/2 ) _a (R ² ₂ SiO _2/2 ) _b (R ³ SiO _3/2 )
_c (SiO _4/2 ) _d (R ⁴ O _1/2 ) _e (HO _1/2 ) _f (wherein R ¹ ,
R ² and R ³ are monovalent hydrocarbon groups selected from the group consisting of alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, and aryl groups having 6 to 12 carbon atoms. , The content of aryl groups in R ³ is 20 to 100 mol%.
Is within the range of. R ⁴ is an alkyl group. a, b,
d, e, and f are 0 or a positive number, and c is a positive number. ) Branched organopolysiloxane (0.
01 to 20 parts by weight), a flame-retardant organic resin composition. 2. The flame-retardant organic resin composition according to claim 1, wherein the component (A) is an aromatic polycarbonate resin. 3. The flame-retardant organic resin composition according to claim 1, wherein the epoxy group in the component (B) is bonded to a silicon atom as a γ-glycidoxypropyl group. 4. The component (C) has an average molecular formula: (R ² ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d (R ⁴ O
_1/2 ) _e (HO _1/2 ) _f (wherein R ² and R ³ have 1 to 1 carbon atoms)
A monovalent hydrocarbon group selected from the group consisting of an alkyl group having 2 to 2 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms, and containing an aryl group in R ^3. The amount is in the range of 20 to 100 mol%. R ⁴ is an alkyl group. b, d, e, f are 0 or a positive number, and c is a positive number. ) Is a branched organopolysiloxane represented by the formula (1), the flame-retardant organic resin composition according to claim 1. 5. The component (C) has an average molecular formula: (R ² ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c (HO _1/2 ) _f (wherein
R ² and R ³ are monovalent hydrocarbon groups selected from the group consisting of alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, and aryl groups having 6 to 12 carbon atoms. , The content of aryl groups in R ³ is 20 to 100 mol%.
Is within the range of. b and f are 0 or a positive number, and c is a positive number. ) Is a branched organopolysiloxane represented by the formula (1), the flame-retardant organic resin composition according to claim 1. 6. The component (C) has an average molecular formula: (R ³ SiO _3/2 ) _c (HO _1/2 ) _f (wherein R ³ has 1 carbon atom).
12 alkyl group, ant 6-12 alkenyl groups and carbon atoms of 2 to 12 carbon atoms - is a monovalent hydrocarbon radical selected from the group consisting of group, ants in R ³ - Le group The content is in the range of 20 to 100 mol%. c is a positive number and f is 0 or a positive number. ) Is a branched organopolysiloxane represented by the formula (1), the flame-retardant organic resin composition according to claim 1. 7. The weight average molecular weight of the component (C) is from 300 to 300.
The flame-retardant organic resin composition according to claim 1, wherein the flame-retardant organic resin composition is 10,000. 8. The method further comprises (D) an alkali metal salt of an organic acid or an organic acid ester, or an alkaline earth metal salt of an organic acid or an organic acid ester (0.02 to 1 part by weight). The flame-retardant organic resin composition according to claim 1. 9. Further, (E) fluororesin powder (0.0
1 to 5 parts by weight).
Alternatively, the flame-retardant organic resin composition according to claim 8.