JP2003277596A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition comprising an aromatic polycarbonate and a styrene resin and using a highly safe organopolysiloxane, the composition showing excellent flame retardance when molded into an article with a thin wall thickness, although it comprises a highly flammable styrene resin as a resin component. <P>SOLUTION: This resin composition comprises 100 pts.wt. of a resin component (A) comprising 50-95 wt.% of an aromatic polycarbonate and 50-5 wt.% of a styrene resin, 0.1-15 pts.wt. of a specific organopolysiloxane (B), and 0.05-5 pts.wt. of a potassium and/or sodium perfluoroalkanesulfate (C). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retarded resin composition, more specifically, an aromatic polycarbonate resin composition flame-retarded with an organopolysiloxane having a specific structure and a specific metal sulfonate. Regarding things.

[0002]

2. Description of the Related Art Aromatic polycarbonate has impact resistance,
It is known as an engineering plastic excellent in heat resistance and transparency, and is widely used particularly in the fields of office automation equipment, home electric appliances and information communication equipment. Further, in these fields, in order to cope with the complicated and thin parts shape, styrene resin is blended with aromatic polycarbonate to improve the melt flowability of aromatic polycarbonate and enhance injection moldability. Many things are done. As the styrene resin used here, a rubber-modified styrene resin is generally used in consideration of physical properties such as impact resistance.

On the other hand, in such electric / electronic fields, materials used are required to have high flame retardancy in order to enhance the safety of products. Aromatic polycarbonate has a limiting oxygen index of 26 to 27, which is an index of flame retardancy.
And is known to be a self-extinguishing resin.
This is because the main chain of the aromatic polycarbonate molecule is mainly composed of aromatic rings, so that not only thermal decomposition reaction but also rearrangement reaction, cyclization reaction, cross-linking reaction, etc. occur during combustion.
It is considered that this is because a carbonized layer (char) having extremely high flame retardancy can be easily formed.

On the other hand, the styrene resin is a flammable resin having a limiting oxygen index of 18, and it is extremely difficult to prevent its combustion. It is considered that this is because the styrene-based resin is depolymerized by combustion, and the resulting monomer component serves as fuel to continue combustion and accelerate it. Therefore, in the resin mixture of the aromatic polycarbonate and the styrene resin, it becomes more difficult to achieve high flame retardancy as the compounding amount of the styrene resin is increased in order to improve the moldability. Also,
Since the resin becomes easier to burn as the thickness of the molded piece when molded becomes thinner, an extremely advanced flame retardant technique is required for a highly fluid material compatible with thin-wall molding.

As a technique for imparting flame retardancy to a resin, a method of blending a flame retardant aid such as a halogen flame retardant or antimony oxide has been conventionally used. However, due to the recent growing interest in environmental problems, conversion to flame retardants with higher safety is being considered. When imparting flame retardancy to an aromatic polycarbonate or a resin mixture of an aromatic polycarbonate and a styrene resin, a method of using a phosphate ester compound as a flame retardant is generally adopted. However, the phosphoric acid ester compound is easily hydrolyzed and thermally decomposed, and the generated phosphoric acid causes a decrease in the molecular weight of the polycarbonate, which lowers the mechanical properties of the resin. The demand for flame retardants is increasing.

Organopolysiloxane is one of the non-halogen flame retardants that has been studied for a long time because of its high safety. Generally, the organopolysiloxane is a monofunctional unit (M 'unit) represented by the chemical formula (6):

[Chemical 6]

A difunctional unit (D 'unit) represented by the chemical formula (7),

[Chemical 7]

A trifunctional unit (T 'unit) represented by the chemical formula (8), and

[Chemical 8] (R's in the chemical formulas (6) to (8) are each independently a monovalent organic group)

A tetrafunctional unit represented by the chemical formula (4) (Q
unit)

[Chemical 9] It is a polymer containing a plurality of at least one repeating unit selected from the group consisting of:

For example, JP-A-10-139964 (corresponding to European Patent No. 0829521) and JP-A-11-140294 (German Patent No. 19850).
(Corresponding to specification No. 453) discloses a technique in which a branched organopolysiloxane having D units and T units as main constituent units and optionally Q units is used as a flame retardant for aromatic polycarbonate.

However, since the effect of improving the flame retardancy when the organopolysiloxane is used alone is insufficient, many techniques of using other flame retardants in combination with the organopolysiloxane have been studied. As the flame retardant used in combination, an organic metal salt represented by an aromatic sulfonic acid metal salt or a perfluoroalkane sulfonic acid metal salt is generally used, and further, it prevents dripping of combustion particles generated during combustion. Therefore, a fluorinated olefin resin such as polytetrafluoroethylene is often added.

For example, JP-A-11-217494 (corresponding to European Patent No. 1035169) and JP-A-2
000-302961 (International Publication No. 2000/6
(Corresponding to the pamphlet of 4976), JP 2000-22
Japanese Patent No. 6527, JP 2001-200150 A, etc. mainly describe organopolysiloxanes having various branched structures composed of D units, T units and Q units,
A technique is disclosed in which a polycarbonate resin is used in combination with an organic sulfonic acid metal salt and a fluoropolymer.

JP-A-6-306265 and JP-A-6-306265
-336547 (U.S. Pat. No. 5,449,710
(Corresponding to the specification), JP-A-8-176425, JP-A-11-222559 (US Pat. No. 6,18).
(Corresponding to the specification of 4,312), JP-A-11-26390.
No. 3 and Japanese Patent Application Laid-Open No. 2001-26704 also disclose a technique of using an organopolysiloxane having various functional groups and structures in combination with an organic sulfonic acid metal salt as a flame retardant for an aromatic polycarbonate.

In the above-mentioned prior art, the resins used are all aromatic polycarbonates, and there are no concrete examples of the flame retardancy improving effect on a resin mixture comprising an aromatic polycarbonate and a styrene resin. Not disclosed. Presumably, the reason is that the effect of improving the flame retardancy is still insufficient due to the ease of combustion of the styrene resin as described above. As an example describing the technique of using a combination of an organopolysiloxane and a metal salt of an organic sulfonic acid as a flame retardant for a resin mixture composed of an aromatic polycarbonate and a styrene resin,
Japanese Patent Laid-Open No. 2000-191898, International Publication No. 99 /
40158 pamphlet, Japanese Patent Laid-Open No. 2000-1599
96, JP-A 2000-256566, JP-A 2000-345045, and International Publication No. 200.
0/46299 pamphlet, Japanese Patent Laid-Open No. 2001-72
867 publication, JP-A-2002-53746 publication, and the like.

However, in these examples of the prior art, a large amount of organopolysiloxane or metal salt of an organic sulfonic acid is used in order to achieve high flame retardancy while using a styrene resin together. Further, the evaluation of flame retardancy is also carried out using a thick-walled test piece of 2.5 mm or 3.2 mm, which is insufficient for thin-wall molding. Metal salts of organic sulfonic acids represented by perfluoroalkane sulfonic acids and aromatic sulfonic acids, especially alkali metal salts and alkaline earth metal salts, are effective in flame retarding aromatic polycarbonates by adding a small amount. It has been used for a long time (for example, Japanese Patent Publication No.
445, JP-B-57-43099, and JP-B-57-43100).

The action mechanism of the organic sulfonic acid metal salt is described, for example, in G. Journal by Montaud et al.
al of Polymer Science, Po
Lymer Chemistry, Vol. 26, No. 21
The article on page 13 (1988) states that the metal salt of an organic sulfonic acid accelerates the thermal decomposition of the polycarbonate to promote the formation of a carbonized layer. Therefore, in order to cope with the combined use of styrene-based resin, when the amount of the organic sulfonic acid metal salt is increased to increase the flame retardant effect, the thermal stability and the moist heat resistance of the aromatic polycarbonate decrease, and the impact resistance There is a problem that mechanical properties such as properties are likely to be impaired.

As described above, the composition is safe against a resin composition composed of an aromatic polycarbonate and a styrene resin, and
There is still no technology capable of imparting a high degree of flame retardancy, and its development is required.

[0018]

In view of the above situation, the present invention is a composition containing an aromatic polycarbonate and a styrene resin, which uses a highly safe organopolysiloxane, and is burned into a resin component. It is an object of the present invention to provide a resin composition that exhibits excellent flame retardancy even when it is molded into a thin wall, even though it contains a styrenic resin having high properties.

[0019]

As a metal salt of an organic sulfonic acid, which has been generally used for flame retarding a resin mixture comprising an aromatic polycarbonate and a styrene resin, potassium perfluorobutane sulfonate is representative. Perfluoroalkane sulfonic acid alkali (earth) metal salts, aromatic diphenyl sulfone-3-sulfonate and aromatic parasulfonic acid alkali (earth) metal salts typified by sodium paratoluene sulfonate, sulfonamide Alkaline (earth) metals such as sulfonylimides were sometimes used.

However, the superiority or inferiority of the effects of these different organic sulfonic acid metal salts has hardly been discussed so far. Further, when used in combination with an organopolysiloxane, the superiority or inferiority of the effect produced by various combinations of the organic sulfonic acid metal salt and the organopolysiloxane has hardly been discussed so far.
Therefore, in order to achieve the object of the present invention, the present inventors have
We have conducted intensive research focusing on the combination of the structure of the organopolysiloxane and the structure of the organic sulfonic acid metal salt used together. As a result, surprisingly, by using an organopolysiloxane having a specific structure in combination with potassium and / or sodium perfluoroalkanesulfonate, an excellent synergistic effect which has never been achieved is exhibited, and an aromatic polycarbonate is obtained. They have found that a resin mixture composed of a styrene resin can be imparted with a high degree of flame retardancy, and have completed the present invention.

That is, the present invention is as follows. [1] 0.1 to 15 parts by weight of organopolysiloxane (B) and per 100 parts by weight of a resin component (A) consisting of 50 to 95% by weight of aromatic polycarbonate and 50 to 5% by weight of styrene resin. Fluoroalkanesulfonate potassium and / or sodium (C)
A resin composition comprising 0.05 to 5 parts by weight, wherein the organopolysiloxane (B) is a monofunctional siloxane unit (M unit) represented by the chemical formula (1), (wherein R is each Independently, an alkyl group having 1 to 8 carbon atoms and 6 to 8 carbon atoms
A monovalent hydrocarbon group selected from the group consisting of 12 unsubstituted or substituted aromatic groups)

[0022]

[Chemical 10]

A difunctional repeating siloxane unit (D unit) represented by the chemical formula (2),

[Chemical 11] (In the formula, R is the same as the chemical formula (1))

A trifunctional repeating siloxane unit (T unit) represented by the chemical formula (3),

[Chemical 12] (In the formula, R is the same as the chemical formula (1))

And a tetrafunctional repeating siloxane unit (Q unit) represented by the chemical formula (4)

[Chemical 13]

The content of each unit in the organopolysiloxane (B) contains at least one selected from the group of M units, D units, T units and Q units in the organopolysiloxane (B). As a standard, M unit is 0-5
0 mol%, D unit 0 to 30 mol%, Q unit 0 to 50
%, And the content of the aromatic group-substituted trifunctional repeating siloxane unit (T unit) represented by the chemical formula (5) is 50 to 100 mol%. .

[0027]

[Chemical 14] (In the formula, R ′ is a monovalent unsubstituted or substituted aromatic group having 6 to 12 carbon atoms)

[2] The resin composition according to [1], wherein the potassium and / or sodium perfluoroalkanesulfonate (C) is potassium trifluoromethanesulfonate and / or sodium trifluoromethanesulfonate. . [3] The hydrocarbon groups R in the chemical formulas (1), (2) and (3) are each independently selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an isopropyl group and a phenyl group, and The resin composition according to [1] or [2], wherein the aromatic group R ′ of the chemical formula (5) is a phenyl group.

[4] Aromatic polycarbonate 50 to 9
To 100 parts by weight of the resin component (A) composed of 5% by weight and 50 to 5% by weight of the styrene resin, 0.01% of the fluoroolefin resin (D) was further added as a drip-preventing agent.
To 3 parts by weight, the resin composition according to any one of [1] to [3].

The present invention will be described in detail below. The resin component (A) used in the present invention comprises a resin mixture of an aromatic polycarbonate and a styrene resin. In the present invention, the aromatic polycarbonate used as the resin component (A) has a main chain composed of a repeating unit represented by the chemical formula (9),

[0031]

[Chemical 15] (In the formula, Ar represents a divalent phenolic compound residue)

It is produced by a reaction of a dihydric phenol compound and a carbonate precursor, polymerization of a carbonate prepolymer, or the like. Specifically, an interfacial polymerization method (phosgene method) in which a dihydric phenol compound and phosgene are reacted in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent, an ester which reacts the dihydric phenol compound and diphenyl carbonate Those produced by methods such as an exchange method (melting method) and a solid-phase polymerization method using a crystallized carbonate prepolymer can be used.

Examples of dihydric phenol compounds include 2,2
-Bis (4-hydroxyphenyl) propane [bisphenol A], 2,2-bis (4-hydroxy-3,5-
Dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, 4,4′-dihydroxydiphenyl, 4,
4'-dihydroxy-3,3 ', 5,5'-tetramethyldiphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4
-Hydroxyphenyl) ethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl)
Ketone, bis (4-hydroxyphenyl) sulfide,
Bis (4-hydroxyphenyl) sulfone, bis (4-
Hydroxyphenyl) sulfoxide, hydroquinone,
Resorcinol, catechol, etc. are mentioned, especially 2,2
-Bis (4-hydroxyphenyl) propane [bisphenol A] is preferred. These dihydric phenol compounds may be used alone or in combination of two or more.

In order to control the molecular weight of the aromatic polycarbonate, the polymerization reaction for producing the aromatic polycarbonate is carried out by phenol, p-methylphenol, m-methylphenol, p-propylphenol, m-propylphenol, p-. It may be carried out in the presence of a monohydric phenol compound such as t-butylphenol, pt-octylphenol and p-cumylphenol. The aromatic polycarbonate used in the present invention may have a branched structure. The aromatic polycarbonate having a branched structure can be produced by the same method as the above-mentioned method for producing an aromatic polycarbonate, except that the polymerization reaction is carried out in the presence of a branching agent.

Examples of branching agents are 1,1,1-tris (4-hydroxyphenyl) ethane, 1,3,5-tris (4-hydroxyphenyl) benzene, α, α ',
α ″,-tris (4-hydroxyphenyl) -1,3
5-triisopropylbenzene, phloroglucin, 4,
6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 4,6-dimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, isatin bisphenol [3,3-bis (4-hydroxyphenyl) oxindole] and the like can be mentioned.

The aromatic polycarbonate used in the present invention preferably has substantially no halogen in its structure. From the viewpoint of mechanical strength and moldability, the viscosity average molecular weight is preferably 10,000 to 100,000, more preferably 14,000 to 40,000. The viscosity average molecular weight of the aromatic polycarbonate can be determined by converting the solution viscosity (using methylene chloride as a solvent).

In the present invention, the styrene resin used as the resin component (A) is a rubber-modified styrene resin and / or a rubber non-modified styrene resin, and particularly, a rubber-modified styrene resin alone or a rubber-modified styrene resin. And a rubber-unmodified styrenic resin are preferred. The rubber-modified styrenic resin refers to a polymer in which a rubber-like polymer is dispersed in particles in a matrix made of a styrene-based resin. In the presence of the rubber-like polymer, styrene, α-
Aromatic vinyl monomer such as methylstyrene and p-methylstyrene, or, if desired, a monomer mixture obtained by adding the above aromatic vinyl monomer to another monomer copolymerizable therewith. Is obtained by graft (co) polymerization by a known polymerization method such as bulk polymerization, emulsion polymerization and suspension polymerization.

Examples of the rubber-like polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), isoprene rubber, chloroprene rubber, acrylic rubbers such as polybutyl acrylate, ethylene. Examples thereof include a propylene-diene monomer terpolymer (EPDM), an ethylene-octene copolymer rubber, and a composite rubber (silicon / acrylic composite rubber) containing an organopolysiloxane component and an alkyl (meth) acrylate component.

Examples of other monomers copolymerizable with the above aromatic vinyl monomer include unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid, alkyl acrylate and methacrylic acid. Examples thereof include vinyl acid monomers such as alkyl acid salts, maleic anhydride, and N-substituted maleimides. The content of the rubber-like polymer in the rubber-modified styrenic resin is usually 5 to 80% by weight, preferably 10 to 60% by weight. If the content of the rubber-like polymer is less than 5% by weight, the impact resistance of the resin composition tends to be insufficient, and if it exceeds 80% by weight, the rigidity and thermal stability are deteriorated and the melt fluidity is deteriorated. Problems such as gel generation and coloring are likely to occur.

The average particle size of the rubber-like polymer in the rubber-modified styrene resin is preferably 0.1 to 2.0 μm, more preferably 0.1 to 1.0 μm, most preferably 0.2 to 1.0 μm.
It is 0.6 μm. When the average particle size is less than 0.1 μm,
It becomes difficult to sufficiently improve the impact resistance of the resin composition, and when it exceeds 2.0 μm, the fluidity of the resin composition and the appearance of the molded product are likely to be deteriorated. As a preferable example of the rubber-modified styrenic resin, high impact polystyrene (HI
PS), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES
Resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), and the like. Also silicon
A composite rubber-based graft copolymer obtained by grafting the vinyl monomer onto an acrylic composite rubber can also be used as the rubber-modified styrene-based resin.

The rubber-unmodified styrenic resin is obtained by the same method as that for the rubber-modified styrenic resin except that the rubber-like polymer is not used. That is, aromatic vinyl monomers such as styrene, α-methylstyrene and p-methylstyrene, and unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid and acrylic acid, if desired. It is a polymer obtained by (co) polymerizing vinyl monomers such as alkyl, alkyl methacrylate, maleic anhydride, and N-substituted maleimide. Examples of the rubber-unmodified styrene-based resin include polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), butyl acrylate-acrylonitrile-styrene copolymer (BAAS resin), and the like.

The reduced viscosity η _{sp of the} matrix resin portion, which is a measure of the molecular weight of the styrene resin used in the present invention.
/ C (0.005 g / cm ³ , under conditions of 30 ° C., measured with a toluene solution when the matrix resin is polystyrene, with a methyl ethyl ketone solution when the matrix resin is an unsaturated nitrile-aromatic vinyl copolymer), 30 ~
It is preferably 80 cm ³ / g, more preferably 40 to 60 cm ³ / g. Examples of means for satisfying the above requirements regarding the reduced viscosity η _sp / c of the styrene resin include adjustment of the amount of polymerization initiator, polymerization temperature, and amount of chain transfer agent.

In the resin component (A) of the present invention, the blending ratio of the aromatic polycarbonate and the styrenic resin is 50 to 95% by weight, preferably 65.
-95% by weight, more preferably 75-90% by weight, styrene resin is 50-5% by weight, preferably 35-5% by weight, more preferably 25-10% by weight. When the aromatic polycarbonate is less than 50% by weight, heat resistance, strength and flame retardancy are poor, and when the styrene resin is less than 5% by weight, moldability is poor.

The organopolysiloxane used as the component (B) of the present invention is one of the components that plays an important role in imparting flame retardancy to the resin component (A).
The organopolysiloxane (B) used in the present invention is
Monofunctional repeating siloxane units (hereinafter referred to as "M units"), difunctional repeating siloxane units (hereinafter referred to as "D units"), trifunctional repeating siloxane units (hereinafter referred to as "T units"), and four It contains at least one selected from a functional repeating siloxane unit (hereinafter referred to as "Q unit").

The content of each unit in the organopolysiloxane (B) is 0 based on the total molar amount of M units, D units, T units and Q units in the organopolysiloxane (B). .About.50 mol%, the D unit is 0 to 30 mol%, the Q unit is 0 to 50 mol%, and the content of the T unit substituted with the aromatic group R ′ is 50 to 100 mol%.
The T unit substituted with the aromatic group R'is a structure which is essential for the organopolysiloxane (B) to impart flame retardancy to the resin component (A), and the content thereof is 50 mol%.
It is necessary that the content be not less than 60 mol%, preferably not less than 60 mol%. If the content is less than 50 mol%, the flame retardancy-providing effect cannot be obtained.

The organopolysiloxane (B) may further contain another T unit in addition to the T unit substituted with the aromatic group R '. The D unit is a unit that forms a linear structure, but if the content of the D unit is increased, the organopolysiloxane (B) tends to be liquid at room temperature, resulting in poor handleability or in the resin component (A). It is not preferable because the dispersibility of is decreased. Further, since the D unit is easily decomposed during combustion and easily forms a cyclic polysiloxane and scatters out of the system, it hardly contributes to imparting flame retardancy to the resin component (A). For this reason, the content of the D unit needs to be 30 mol% or less, and preferably 20 mol% or less.

Regarding the contents of M unit and Q unit,
Any of them can be used optionally in the range of 0 to 50 mol%. M
Since the unit is a unit constituting the terminal group, the molecular weight of the organopolysiloxane (B) decreases as the content thereof increases, and the organopolysiloxane (B) tends to scatter during combustion, resulting in a decrease in flame retardancy of the resin composition. There is. Therefore, the content of the M unit is preferably 0 to 40 mol%. Q unit is
It is a unit that forms a crosslinked structure, and if its content increases, gelation may occur during the production of the organopolysiloxane (B), or the molecular weight of the organopolysiloxane (B) may become too high, resulting in the resin component (A). In some cases, the dispersibility in the composition is reduced and the flame retardancy-imparting effect is reduced. Therefore, the content of the Q unit is preferably 0 to 40 mol%.

The organic group R in the M unit, D unit and T unit constituting the organopolysiloxane (B) of the present invention is
Each of them is independently a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and an unsubstituted or substituted aromatic group having 6 to 12 carbon atoms. The substituent R ′ in the aromatic-substituted T unit is a monovalent unsubstituted or substituted aromatic group having 6 to 12 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t
Examples include -butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and isooctyl group.

Examples of the unsubstituted or substituted aromatic group having 6 to 12 carbon atoms are phenyl group, tolyl group, xylyl group,
Examples thereof include naphthyl group and biphenyl group. Among these, as an alkyl group, a methyl group, an ethyl group, n
-Using a group selected from the group consisting of propyl group and isopropyl group, using a phenyl group as an aromatic group,
It is preferable from the viewpoint of further exhibiting the performance as a flame retardant and the economical efficiency.

The mixing ratio of the organopolysiloxane (B) is 0.1 to 15 relative to 100 parts by weight of the resin component (A).
Parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight. If the blending ratio of the organopolysiloxane (B) is less than 0.1 part by weight, the flame retardancy improving effect is poor. On the other hand, when it exceeds 15 parts by weight, mechanical properties such as impact resistance are deteriorated and moldability is deteriorated. The organopolysiloxane (B) may be used alone, 2
You may use together more than one kind.

The method for producing the organopolysiloxane (B) is not limited, and known methods can be used. For example, it can be obtained by subjecting an organochlorosilane, an organoalkoxysilane or the like to hydrolysis polycondensation using an acid and / or base catalyst in the presence of a theoretical or excess amount of water. At that time, the content of M units, D units, T units, and Q units is controlled by adjusting the structures of the organochlorosilanes, organoalkoxysilanes, and the like to be used and the blending amounts thereof to control the organopolypolysiloxane having a desired branched structure. Siloxane (B) can be obtained. Further, the molecular weight of the organopolysiloxane (B) can be adjusted by adjusting the type and amount of the catalyst used, the amount of water, the temperature and time of the hydrolysis polycondensation reaction, the amount of M unit introduced, and the like.

The branched structure of the organopolysiloxane (B) is not limited as long as the content of M unit, D unit, T unit and Q unit is within the above range, and various types can be used. For example, a branched structure consisting of only T units, D / T, T
A branched structure composed of each combination of / Q and D / T / Q is included. M / T, M / D / T, M / T / Q, and M / D as a structure introduced with an end group consisting of M units
A branched structure composed of each combination of / T / Q can be mentioned.

The preferred structure of the organopolysiloxane (B) is a branched structure composed of T, D / T, M / T or a combination of M / D / T, and may be branched, ladder or cage. preferable. When the organopolysiloxane (B) is produced by using a combination selected from D units, T units and Q units without using M units, hydroxyl groups and / or alkoxy groups directly bonded to silicon atoms may remain as terminal groups. The alkyl group in the alkoxy group depends on the starting material for the production of the organopolysiloxane (B) and the solvent used for the production, and is usually a methyl group,
It is a lower alkyl group such as an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group.

Since these terminal groups, especially the hydroxyl group, have high reactivity, when they are present in a large amount in the organopolysiloxane, they are hydrolyzed and then crosslinked to reduce the moldability of the resin composition. When compounded in the resin component, it may not be preferable because it may react with the aromatic polycarbonate at a high temperature to cause a side reaction such as a decrease in the molecular weight of the aromatic polycarbonate. In such a case, the terminal hydroxyl group can be converted into M units by treating with a silylating agent described later to stabilize the organopolysiloxane (B).

The introduction of M units into the skeleton of the organopolysiloxane (B) can be carried out not only in such a silylation treatment after the hydrolysis polycondensation but also at the same time during the hydrolysis polycondensation. Specific examples of the organochlorosilane, organoalkoxysilane, and other raw materials used for producing the organopolysiloxane (B) include the following.

As the raw material of the D unit, dimethyldichlorosilane, diethyldichlorosilane, methylphenyldichlorosilane, diphenyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylphenyldimethoxysilane, Examples thereof include methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like.

As a raw material of the D unit other than the above, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,
3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,
3,5,7-tetraphenylcyclotetrasiloxane,
Examples include hexaphenylcyclotrisiloxane and octaphenylcyclotetrasiloxane.

As the raw material of the T unit, methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, isopropyltrichlorosilane, phenyltrichlorosilane, isooctyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane,
Examples thereof include isopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, isooctyltrimethoxysilane, and isooctyltriethoxysilane.

Examples of the raw material for the Q unit include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane and the like. Examples of the silylating agent for introducing the M unit include chlorosilanes such as trimethylchlorosilane, triethylchlorosilane, dimethylphenylchlorosilane, diphenylmethylchlorosilane and triphenylchlorosilane, and disilazane such as hexamethyldisilazane.

Examples of M unit raw materials other than the above silylating agent include hexamethyldisiloxane and 1,3-diphenyltetramethyldisiloxane. The content of terminal hydroxyl groups in the organopolysiloxane (B) is preferably 5% by weight or less, more preferably 1% by weight or less. The content of the terminal alkoxy group in the organopolysiloxane (B) is preferably 10% by weight or less, more preferably 5% by weight or less.

The hydroxyl group content can be determined, for example, by a method of quantifying the amount of gas generated when the reaction is carried out with an organometallic compound such as alkyllithium or alkylmagnesium halide (Grignard reagent) in an anhydrous solvent. The content of the alkoxy group can be calculated, for example, from the signal area ratio of the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum in combination with an appropriate internal standard substance. The weight average molecular weight of the organopolysiloxane (B) is 500 to 100,000.
0 is preferable, 1,000 to 40,000 is more preferable, and 1,000 to 10,000 is the most preferable.

If the weight average molecular weight is less than 500, the volatility of the organopolysiloxane (B) becomes high and the organopolysiloxane (B) tends to scatter during combustion, resulting in a decrease in the flame retardancy of the resin composition. Conversely, the weight average molecular weight is 100,000.
When it exceeds the above range, the dispersibility of the organopolysiloxane (B) in the resin component (A) decreases, the flame retardancy of the resin composition becomes insufficient, and the mechanical properties of the resin composition tend to deteriorate. The potassium and / or sodium perfluoroalkane sulfonate used as the component (C) of the present invention is a component that characterizes the present invention, and has a synergistic effect with the organopolysiloxane (B) with respect to the resin component (A). Plays an important role in imparting flame retardancy.

Conventionally, in order to make an aromatic polycarbonate flame-retardant, perfluoroalkanesulfonic acid alkali (earth) salts typified by potassium perfluorobutanesulfonate and diphenylsulfone- are used as organic sulfonic acid metal salts.
Alkali aromatic sulfonates (earth) represented by potassium 3-sulfonate and sodium paratoluenesulfonate
Salt has been widely used. When the present inventors searched for an organic sulfonic acid metal salt suitable for flame retarding a resin composition comprising an aromatic polycarbonate and a styrene resin, an aromatic sulfonic acid metal salt or an aliphatic sulfonic acid metal salt is effective. However, it was found that the perfluoroalkane sulfonic acid metal salt was more effective than the above.

Furthermore, when the metal salts of perfluoroalkane sulfonic acid were compared and examined, it was found that potassium and sodium salts of perfluoroalkane sulfonic acid, especially trifluoromethane sulfonic acid, were present in the presence of an organopolysiloxane having a specific structure. It has been found that potassium and sodium trifluoromethanesulfonate exhibit extremely excellent effects and are suitable for the purpose of the present invention. Such a synergistic effect of potassium trifluoromethanesulfonate or sodium trifluoromethanesulfonate and an organopolysiloxane has not been known at all in the past, which was an unexpected result.

As the potassium and / or sodium perfluoroalkanesulfonate used as the component (C) of the present invention, potassium trifluoromethanesulfonate and sodium trifluoromethanesulfonate are most preferable, and potassium perfluoroethanesulfonate and perfluoromethane are preferable. Sodium ethanesulfonate, potassium perfluoropropanesulfonate, sodium perfluoropropanesulfonate, potassium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, potassium perfluorooctanesulfonate, sodium perfluorooctanesulfonate, etc. can also be used. .

The mixing ratio of potassium and / or sodium perfluoroalkanesulfonate (C) is 0.05 to 5 parts by weight based on 100 parts by weight of the resin component (A),
Preferably 0.1 to 2 parts by weight, more preferably 0.1 to
It is in the range of 1 part by weight. If the blending ratio of potassium perfluoroalkanesulfonate and / or sodium (C) is less than 0.05 parts by weight, flame retardancy is not improved. On the other hand, if it exceeds 5 parts by weight, the thermal stability and wet heat resistance of the aromatic polycarbonate are deteriorated, and mechanical properties such as impact resistance are deteriorated.

In order for potassium and / or sodium perfluoroalkanesulfonate (C) to exert its effect, as described above, the aromatic group-substituted T unit is contained in a specific ratio, and the D unit is contained. It is essential to use it in combination with the organopolysiloxane (B) whose ratio is not more than a specific amount.
The reason for this is not clear at this time, but it can be inferred as follows, for example. The potassium and sodium salts of perfluoroalkane sulfonic acids are described in G. M
Journal of Pol by ontaudo et al.
ymer Science, Polymer Che
mystry, 26, 2113 (1988)
, Which promotes rearrangement / crosslinking reactions of polycarbonate at high temperatures, and promotes the maintenance of the morphology of the burning portion and the formation of a foamed heat insulating layer due to the thickening effect and the like. At this time, when an organopolysiloxane having an aromatic group-substituted T unit coexists, a reaction such that the aromatic group-substituted T unit becomes a reaction point and the organopolysiloxane is incorporated into the crosslinked structure of the polycarbonate occurs, and Si reacts with Si. It is considered that a stronger barrier layer in which polycarbonate is integrated is formed and exhibits an excellent flame retardant effect.

Structures other than T units substituted with aromatic groups,
For example, a T unit substituted with an alkyl group, a T unit substituted with an alkenyl group such as a vinyl group, an M unit, a D unit and a Q unit are reacted so as to exhibit such an excellent flame retardant effect. It is considered to have no sex. In order to obtain an excellent flame retardant effect, the aromatic polycarbonate, the organopolysiloxane, and the sulfonic acid metal salt must undergo thermal decomposition and react with each other. A good balance is considered preferable. When compared among the alkali metal salts, potassium and sodium salts of perfluoroalkane sulfonic acid have higher thermal decomposition temperatures than the lithium salt, the aromatic sulfonic acid alkali metal salt, and the aliphatic sulfonic acid alkali metal salt. Therefore, it is considered to be in a suitable temperature range where the flame retardant effect is exhibited. Among the potassium and sodium salts of perfluoroalkanesulfonic acid, potassium trifluoromethanesulfonate and sodium trifluoromethanesulfonate have a high thermal decomposition temperature suitable for this purpose, and are preferably used.

Even with the same metal salt of perfluoroalkane sulfonic acid, metal salts other than alkali metals do not exhibit an excellent flame retarding effect regardless of the thermal decomposition temperature. It is speculated that this is because the perfluoroalkanesulfonyl group is a strong electron-withdrawing group, and the Lewis acidity or Bronsted acidity of the salt changes due to the change of the metal species, and the action of degrading the polycarbonate becomes stronger. To be done. The fluoroolefin resin used as the component (D) of the present invention is used to prevent the dropping of combustion particles during combustion. The fluoroolefin resin used here is
A homopolymer or a copolymer containing a fluoroethylene structure, for example, a difluoroethylene polymer, a trifluoroethylene polymer, a tetrafluoroethylene polymer,
Examples thereof include a tetrafluoroethylene-hexafluoropropylene copolymer and a copolymer of tetrafluoroethylene and an ethylene-based monomer containing no fluorine. In particular, polytetrafluoroethylene (PTFE) is preferably used,
The molecular weight and morphology are not limited, but it is preferable that they are dispersed in the composition in the form of fibrils having a diameter of 0.5 μm or less.

The amount of the fluoroolefin resin added is preferably 0.01 with respect to 100 parts by weight of the resin component (A).
To 3 parts by weight, more preferably 0.05 to 1 part by weight, and most preferably 0.1 to 0.5 part by weight. If the amount of the fluoroolefin resin added is less than 0.01 part by weight, the effect of preventing dripping is poor, and if it exceeds 3 parts by weight, the fluidity and flame retardancy are reduced.

The resin composition of the present invention can be manufactured by a known method, and the manufacturing method is not limited. For example, the resin component (A), the organopolysiloxane (B), and potassium and / or sodium perfluoroalkanesulfonate (C) and, if necessary, the fluoroolefin resin (D) are further preliminarily mixed, and then the resin component (A)
Melt-mixing at a temperature equal to or higher than the softening point of the resin component; the resin component (A), potassium and / or sodium perfluoroalkanesulfonate (C) and, if necessary, the fluoroolefin resin (D) are premixed and further melted After the state, a method of mixing the organopolysiloxane (B); the organopolysiloxane (B) and potassium and / or sodium perfluoroalkanesulfonate (C), and if necessary, a fluoroolefin resin (D)
Is mixed with the resin component (A) in the molten state after premixing; organopolysiloxane (B) and potassium and / or sodium perfluoroalkanesulfonate (C); and, if necessary, fluoroolefin resin (D). )
And a part of the resin component (A) are mixed in advance to form a masterbatch, and the resulting mixture is added to the rest of the resin component (A).

As the premixing method, a dry blending method; a method using a Henschel mixer, a super mixer, a tumble mixer, a ribbon blender or the like; (A) to
A wet method in which a part or all of the component (C) is dissolved in water or a solvent, mixed, and then dried can be used. As a method for melt mixing, a method using a single screw extruder, a twin screw extruder, a Banbury mixer, a Brabender, or the like can be used.

In order to impart a higher degree of flame retardancy to the resin composition, it is necessary to use a resin other than the organopolysiloxane (B), potassium and / or sodium perfluoroalkanesulfonate (C) and the fluoroolefin resin (D). It is also possible to use a combustible component together. For example, a) a phosphate ester compound, b) an inorganic phosphorus compound such as red phosphorus and ammonium polyphosphate, c) a halogen organic compound,
d) Nitrogen-containing organic compounds such as melamine, melamine cyanurate, melam, melem, melon, etc. e) Magnesium hydroxide, calcium hydroxide, aluminum hydroxide, hydrotalcite, zinc borate, zinc stannate, antimony oxide, oxidation Inorganic metal compounds such as molybdenum, titanium oxide, zirconium oxide and zinc oxide, f) polyphenoxyphosphazene, polytolyloxyphosphazene, polymethoxyphosphazene, polyphenoxymethoxyphosphazene, polyphenoxytolyloxyphosphazene and the like,
One selected from cyclic or linear phosphazene polymers or oligomers, g) phenols such as phenol, cresol, t-butylphenol, phenylphenol, and phenol resin such as novolak resins and resole resins produced from formaldehyde. Alternatively, two or more compounds are used. Among these, a) phosphoric acid ester compounds, which are relatively less toxic and less deteriorated in physical properties, are preferable.

Examples of the a) phosphoric acid ester compounds include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triphenyl phosphate, tritolyl phosphate, trixylyl phosphate, dimethyl ethyl phosphate. Examples include phosphoric acid esters such as methyl dibutyl phosphate, ethyl dipropyl phosphate, and hydroxyphenyl diphenyl phosphate, compounds in which various substituents are introduced, and condensed phosphoric acid ester compounds represented by the following formula (10). .

[0075]

[Chemical 16] (In the formula, n is an integer of 1 to 10, Ar ¹ , Ar ² , and A.
r ⁴ and Ar ⁵ are each independently

An aromatic group selected from a phenyl group which is unsubstituted or substituted with at least one hydrocarbon group having 1 to 10 carbon atoms, and Ar ³ is a divalent aromatic group having 6 to 20 carbon atoms) Examples of the condensed phosphoric acid ester-based compound include bisphenol A tetraphenyl diphosphate, bisphenol A tetratolyl diphosphate, bisphenol A tetraxylyl diphosphate, and bisphenol A.
Di (phenylxylyl phosphate), resorcinol tetraphenyl diphosphate, and resorcinol tetraxylyl diphosphate are preferably used.

The flame-retardant resin composition of the present invention has moldability,
For the purpose of improving impact resistance, rigidity, weather resistance, appearance, etc., various additives commonly used in thermoplastic resins can be added. Examples of additives include heat stabilizers, antioxidants, ultraviolet absorbers, weathering agents, antibacterial agents, compatibilizers, colorants (dye, pigment), release agents, lubricants, antistatic agents, plasticizers,
Examples thereof include dispersants, polymers such as other resins and rubbers, and fillers. The amount added is not limited as long as the characteristics of the flame-retardant resin composition of the present invention are maintained.

The flame-retardant resin composition of the present invention is used in copying machines, fax machines, televisions, radios, tape recorders, video decks, personal computers, printers, telephones, information terminals,
It is preferably used for OA devices such as mobile phones, refrigerators and microwave ovens, information / communication devices, electric / electronic devices, housings of home appliances or various parts thereof, and automobile parts.

[0079]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these. The following components were used in the examples and comparative examples. (A-1) Aromatic polycarbonate PC: Bisphenol A polycarbonate manufactured by Mitsubishi Engineering Plastics Co., Ltd. (Iupilon (registered trademark) S3000, viscosity average molecular weight 20,000) (A-2) Styrenic resin AS: Asahi Kasei Corporation Acrylonitrile-styrene copolymer (Styrac AS (registered trademark) T8801) ABS: Mitsubishi Rayon Co., Ltd. powdery acrylonitrile-butadiene-styrene copolymer RV

(B) Organopolysiloxane The following organopolysiloxane was used. These structures are shown in Table 1. S-1: SLJ1447A manufactured by Wacker of Germany S-2: SLJ1447B manufactured by Wacker of Germany S-3: SLJ1447D of Wacker of Germany S-4: Using phenyltrichlorosilane and methyltrichlorosilane, JP 2001-200150 A. Synthesized according to the method described in the publication. S-5: Tetraethoxysilane having a SiO ₂ component of 40% TES40 (manufactured by Wacker, Germany), hexamethyldisiloxane and phenyltriethoxysilane were used in the method described in JP-B-8-22921. Therefore, it is a composite. S-6: German Wacker SLJ1447E S-7: German Wacker Resin MK S-8: German Wacker MQ-Resin 803 S-9: Gelest PMM0025 S-10: Phenyltrichlorosilane and A compound synthesized by using methyltrichlorosilane according to the method described in JP 2001-200150 A. S-11: Synthesized using phenyltrichlorosilane and vinyltrichlorosilane according to the method described in JP 2001-200150 A. In addition to the above, KR219 manufactured by Shin-Etsu Chemical Co., Ltd. was used as an organopolysiloxane having a phenyl group, a vinyl group and a methoxy group. The content of the phenyl group determined by using ¹ H-NMR was about 35 mol%. The weight average molecular weight of the organopolysiloxane (B) was determined by gel permeation chromatography (GPC) as a polystyrene-equivalent weight average molecular weight.

(C) Potassium perfluoroalkanesulfonate and potassium sodium trifluoromethanesulfonate: sodium trifluoromethanesulfonate manufactured by Wako Pure Chemical Industries, Ltd .: potassium perfluorobutanesulfonate manufactured by Tokyo Chemical Industry Co., Ltd .: Dainippon Ink Chemical Industry Co., Ltd. Megafac (registered trademark) F114P In the comparative example, the following commercially available sulfonic acid metal salts were used. KSS: UCB Japan Co., Ltd. diphenyl sulfone
Potassium 3-sulfonate Sodium paratoluenesulfonate (p-TsON
a): Sodium butanesulfonate manufactured by Wako Pure Chemical Industries, Ltd .: Potassium methanesulfonate manufactured by Wako Pure Chemical Industries, Ltd .: Lithium trifluoromethanesulfonate manufactured by Tokyo Chemical Industry Co., Ltd .: Trifluo manufactured by Tokyo Chemical Industry Co., Ltd. Magnesium methanesulfonate: manufactured by Tokyo Chemical Industry Co., Ltd. Zinc trifluoromethanesulfonate: manufactured by Tokyo Chemical Industry Co., Ltd. Copper (II) trifluoromethanesulfonate: manufactured by Tokyo Chemical Industry Co., Ltd. (D) Fluoroolefin resin Daikin Industries ( Ltd. made PTFE F-201L

The evaluation methods used in the examples and comparative examples of the present invention are as follows. <Izod Impact Strength> According to ASTM D-256, it was measured with a notch and a thickness of 3.2 mm. Samples that did not break were noted as NB. <Thermal Decomposition Temperature of Sulfonic Acid Metal Salt> The decomposition temperature of the sulfonic acid metal salt was determined based on the gas generation behavior measured by the following apparatus and conditions. Equipment: Gas chromatograph with mass spectrometer (Agilen)
HP6890Plus and HP5972N manufactured by t company) Pyrolysis furnace: Double Shot Pyrolyzer (registered trademark) Py-2020D manufactured by Frontier Lab. Co., Ltd. Column: Inert stainless steel tube (2.5 m, inner diameter 0.15 mm, 320 ° C. inlet temperature) Mobile phase: Ultra-high-purity helium gas (0.7 ml / min) Ionization method: Electron impact method Thermal decomposition temperature: Temperature rises from 80 ° C to 650 ° C at 10 ° C per minute Thermal decomposition atmosphere: Ultra-high-purity helium heat When plotting the response of the detector against the temperature of the decomposition furnace, a curve corresponding to the amount of gas generated in the decomposition furnace is obtained, but this curve shows the maximum when measured with metal sulfonate as a sample. Was used as the decomposition temperature of the salt.

[0083]

Examples 1 to 7 The effects of various organopolysiloxanes having T units substituted with phenyl groups were confirmed. Aromatic polycarbonate, styrenic resin, organopolysiloxane, and potassium trifluoromethanesulfonate or potassium perfluorobutanesulfonate (F
114P) was weighed into a polyethylene bag with the composition shown in Table 2 and premixed by manual mixing. Extruder (KZ manufactured by Techno Bell, Japan
(W15-45 MG) was melt-kneaded at 250 ° C. The resin composition (pellet) thus obtained was used in a small injection molding machine (MJEC10) manufactured by Modern Machinery Co., Ltd. of Japan for 25
Molding was performed at 0 ° C. to prepare a test piece having a thickness of 3.2 mm.

A vertical burning test according to UL-94 was carried out using the prepared test piece to evaluate the self-extinguishing property of the resin composition. The results are shown in Table 2. As is clear from Table 2, the resin composition of the present invention does not cause the dropping of combustion particles,
All show excellent flame retardancy (self-extinguishing properties).

[0085]

[Comparative Example 1] Examples 1 to 1 except that a test piece was prepared using only an aromatic polycarbonate and a styrene resin without using an organopolysiloxane and a metal sulfonate.
The same operation as in 7 was performed. The results are shown in Table 2. Table 2
As is clear from the above, combustion particles were dropped and the combustion time was long.

[0086]

[Comparative Example 2] The same as Examples 1 to 7 except that a test piece was prepared using a resin mixture containing an aromatic polycarbonate, a styrene resin and an organopolysiloxane S-2 without using a metal sulfonate. The operation was performed. The results are shown in Table 2. As is clear from Table 2, combustion particles were dropped and the combustion time was long. From this result, it is understood that the effect of improving the flame retardancy is insufficient only with the organopolysiloxane.

[0087]

Comparative Example 3 The same operations as in Examples 1 to 7 were carried out except that a test piece was prepared using a resin mixture containing an aromatic polycarbonate, a styrene resin and potassium trifluoromethanesulfonate, without using the organopolysiloxane. went. The results are shown in Table 2. As is clear from Table 2, combustion particles were dropped and the combustion time was long. From this result, it can be seen that the sulfonic acid metal salt alone has no effect of improving flame retardancy.

[0088]

[Comparative Example 4] The D unit was 3 as the organopolysiloxane.
Using S-6 having 8 mol%, flame retardancy was evaluated by the same composition and method as in Examples 1 to 7. The results are shown in Table 2. It can be seen that the effect of imparting flame retardancy is remarkably inferior as compared with Example 3 using S-3 containing 20 mol% of D unit.

[0089]

Comparative Examples 5 to 8 Examples 1 to 7 were prepared using organopolysiloxanes S-7 to S-10 which did not contain any T units substituted with phenyl groups or whose content was less than 50 mol%.
Flame retardancy was evaluated in the same manner as in. In Comparative Examples 5 and 6, the addition amount of organopolysiloxane was increased as shown in Table 2 and evaluated. The results are shown in Table 2. As is clear from this table, all were extremely inferior in the flame retardancy imparting effect.

[0090]

Comparative Example 9 The effect of the organopolysiloxane KR219 disclosed in JP-A-2000-191898 was evaluated by the same composition and method as in Examples 1-7. The results are shown in Table 2. As is clear from this table, Comparative Example 9 is significantly inferior in the flame retardancy imparting effect. It is considered that this is because the content of the phenyl group is low and that the vinyl group contains a crosslinkable functional group.

[0091]

Example 8, Comparative Examples 10 to 14 Using S-2 or S-3 as the organopolysiloxane, the effects of various alkali metal sulfonates were evaluated. The composition and the evaluation method were in accordance with Examples 1 to 7. The results of the flame retardancy evaluation results are shown in Table 3. Examples 2, 3 and 7 in Table 3
Is the same as the result already shown in Table 2. Also,
The thermal decomposition temperature of the sulfonic acid metal salt is shown in the table. Table 3
Based on, when comparing the flammability test results and the thermal decomposition temperature of the alkali metal sulfonate, there is a correlation between the two,
It can be seen that the fluorine-substituted sulfonate having a high thermal decomposition temperature, especially the potassium salt and the sodium salt, are excellent in the flame retardancy imparting effect.

[0092]

[Comparative Examples 15 to 17] S as an organopolysiloxane
-3, the effects of magnesium, zinc and copper (II) salts as sulfonic acid metal salts other than alkali metals were evaluated. The composition and the evaluation method were in accordance with Examples 1 to 7. When either salt is used, the molded pieces are markedly colored,
Further, as shown in Table 3, it is considered that the polycarbonate is decomposed because there is no flame retardance improving effect.

[0093]

Examples 9 to 22 Potassium trifluoromethanesulfonate and potassium perfluorobutanesulfonate (F11
The effect of 4P) was compared in various compositions. Table 4 shows the composition and the evaluation results. In the combustion test, the evaluation method was according to the method described in Examples 1 to 7, except that a test piece having a thickness of 1.6 mm was used. From Table 4, it can be seen that potassium trifluoromethanesulfonate has a better effect than potassium perfluorobutanesulfonate (F114P) over all compositions. It is also found that potassium trifluoromethanesulfonate retains an excellent effect even if the amount used is reduced.

[0094]

Comparative Examples 18 and 19 As the organopolysiloxane,
S-11 containing a vinyl group was used instead of the alkyl group. Table 4 shows the composition and the evaluation results. The evaluation method was in accordance with the method described in Examples 1 to 7 except that a 1.6 mm thick test piece was used in the combustion test. Organopolysiloxane containing a vinyl group is poor in flame retardancy-providing effect, and even if potassium trifluoromethanesulfonate is used, good flame retardancy cannot be obtained.

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

[0099]

EFFECTS OF THE INVENTION The resin composition of the present invention has excellent flame retardancy, and since it uses highly safe organopolysiloxane as a flame retardant, it has a low environmental load. Furthermore, since it is a material that uses a styrene resin in combination, it has good moldability. Therefore, the resin composition of the present invention can sufficiently cope with the increase in size and thickness of office automation equipment, information communication equipment, electric / electronic equipment, home electric appliances, automobile parts, etc., and its application field is expected to expand.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 27:12) F term (reference) 4J002 BC032 BC062 BC072 BC082 BC092 BD124 BD144 BD154 BD164 BN062 BN122 BN142 BN152 BN162 BN172 CG011 CG021 CP033 EV256 FD130 FD133 FD134 FD136 GN00 GQ00

Claims (4)

[Claims] 1. An organopolysiloxane (B) in an amount of 0.1 to 15 parts by weight per 100 parts by weight of a resin component (A) comprising 50 to 95% by weight of an aromatic polycarbonate and 50 to 5% by weight of a styrene resin. And a resin composition containing 0.05 to 5 parts by weight of potassium perfluoroalkanesulfonate and / or sodium (C),
The organopolysiloxane (B) is a monofunctional siloxane unit (M unit) represented by the chemical formula (1), (in the formula, R
Are each independently a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and an unsubstituted or substituted aromatic group having 6 to 12 carbon atoms. A difunctional repeating siloxane unit (D unit) represented by the chemical formula (2): (In the formula, R is the same as the chemical formula (1)) The trifunctional repeating siloxane unit (T unit) represented by the chemical formula (3), (In the formula, R is the same as in the chemical formula (1)) and the tetrafunctional repeating siloxane unit represented by the chemical formula (4) (Q
Unit) [Chemical 4] The content of each unit in the organopolysiloxane (B) is based on the total molar amount of M units, D units, T units and Q units in the organopolysiloxane (B). , M unit is 0 to 50 mol%, D
The unit is 0 to 30 mol%, the Q is 0 to 50 mol%, and the content of the trifunctional repeating siloxane unit (T unit) substituted with an aromatic group represented by the chemical formula (5) is 5
The resin composition is 0 to 100 mol%. [Chemical 5] (In the formula, R ′ is a monovalent unsubstituted or substituted aromatic group having 6 to 12 carbon atoms) 2. The resin composition according to claim 1, wherein the potassium perfluoroalkanesulfonate and / or sodium (C) is potassium trifluoromethanesulfonate and / or sodium trifluoromethanesulfonate. 3. The hydrocarbon groups R in the chemical formulas (1), (2) and (3) are each independently a methyl group, an ethyl group or an n- group.
The resin composition according to claim 1 or 2, wherein the aromatic group R'in the chemical formula (5) is a phenyl group and is selected from the group consisting of a propyl group, an isopropyl group and a phenyl group. 4. A fluoroolefin resin (D) is further added as a drip-preventing agent to 100 parts by weight of a resin component (A) consisting of 50 to 95% by weight of an aromatic polycarbonate and 50 to 5% by weight of a styrene resin. The resin composition according to any one of claims 1 to 3, which comprises 0.01 to 3 parts by weight.