JP2003138121A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition giving a molding having both of excellent flame resistance and good fluidity and also excellent in impact resistance. SOLUTION: This flame retardant resin composition comprises 100 pts.wt. polycarbonate-based resin (A), 0.1-20 pts.wt. silicone compound (B) represented by the average composition formula (1) R<1> m R<2> n SiO(4-m-n)/2 (1) (wherein, R<1> is a 1-4C univalent aliphatic hydrocarbon group; R<2> is a 6-24C univalent aromatic hydrocarbon group; each of R<1> and R<2> be two kinds or more; and m and n are numbers satisfying 1.1<=m+n<=1.7 and 0.4<=n/m<=2.5) and 0.1-20 pts.wt. polyorganosiloxane-containing graft copolymer (C) obtained by graft polymerization of a vinyl-based monomer (c-2) in the presence of a polyorganosiloxane particle (c-1).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polycarbonate resin composition.

[0002]

2. Description of the Related Art Polycarbonate resin has excellent impact resistance, heat resistance, electrical characteristics, etc., and is used for electric / electronic equipment such as OA (office automation) equipment, information / communication equipment, and household electric appliances. It is widely used in various fields such as automobiles and construction. Polycarbonate resin is generally a self-extinguishing resin, but there are fields requiring high flame retardancy, mainly in the fields of electrical and electronic equipment such as OA equipment, information / communication equipment, and home appliances. Improvements have been made by adding various flame retardants. On the other hand, the polycarbonate resin has a high melt viscosity and is inferior in molding fluidity, so that there is a problem that it is difficult to make the molded product thinner and larger.

As a method for improving the flame retardancy of polycarbonate resins, halogenated flame retardants such as halogenated bisphenol A and halogenated polycarbonate oligomers have been used together with flame retardant aids such as antimony oxide from the viewpoint of flame retardant efficiency. . However, in recent years, from the viewpoint of safety and the effect on the environment at the time of disposal / incineration, a flame-retardant method using a flame retardant containing no halogen has been demanded from the market. As the non-halogen flame retardant, there has been proposed a polycarbonate resin composition containing an organic phosphorus flame retardant, particularly an organic phosphate compound.

However, although the phosphoric acid ester compound generally contributes to flame retardancy, there are cases where the molding environment and the appearance of the molded product are not always sufficient, such as mold corrosion and gas generation during molding. Further, it has been pointed out that when the molded product is placed under heating or under high temperature and high humidity, impact strength is lowered and discoloration occurs. Furthermore, there is a problem that the recycling suitability in resource saving in recent years is difficult due to insufficient thermal stability.

On the other hand, silicone compounds have high heat resistance,
Since harmful gas is unlikely to be generated during combustion and the safety of itself is high, many attempts have been made to use it as a flame retardant. As examples of using a silicone compound as a flame retardant, silicone compounds such as those described in JP-A No. 1-318069 and JP-B No. 62-60421 have been tried, but these are large when added alone. Very few have flame retardant effect, and even those that are relatively effective need to be added in large amounts to meet the strict flame retardant standards related to electrical and electronic equipment. As a result, moldability of plastics and kneading It is not practical because it adversely affects the property and other necessary properties and is disadvantageous in cost.

On the other hand, as an attempt to improve the flame-retardant effect of a silicone compound and reduce the addition amount, a method of using a silicone compound and a metal salt in combination has been reported. For this, a combination of polydimethyl silicone with a metal hydroxide and a zinc compound (JP-A-2-150436) and a combination of polydimethyl silicone with a group IIa metal salt of an organic acid (JP-A-56-100853). And silicone resins, especially those represented by M units and Q units, and a combination of silicone oil and a group IIa metal salt of an organic acid (Japanese Patent Publication No. 3-48947), both of which are flame-retardant. There was a fundamental problem that the effect was poor and it was difficult to significantly reduce the addition amount. Further, the use of the metal salt compound generally promotes the decomposition of the resin, so that there is a problem that the surface appearance of the molded body is deteriorated and the resin properties are deteriorated such that the resistance to moist heat is deteriorated.

On the other hand, as a method for improving the molding fluidity of a polycarbonate resin, a method of using a polycarbonate having a relatively low molecular weight, a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, and an acrylonitrile-butadiene-styrene copolymer resin are used. Alloying with polystyrene-based resins such as rubber-modified polystyrene resin has been performed. However, a polycarbonate having a viscosity average molecular weight of 19000 or less has a problem that impact resistance is lowered, and also when alloyed with a crystalline resin such as a polyester resin and a polystyrene resin, the impact resistance is lowered.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition which has a high degree of flame retardancy and good fluidity, and which gives a molded article excellent in impact resistance. It is a thing. This time, the present inventors have examined the correlation between the flame retardancy of the silicone compound and the resin physical properties in detail, and as a result, by adding the silicone compound of the specific structure and the polyorganosiloxane-containing graft copolymer of the specific structure together. Improves impact resistance even when used for low molecular weight grade resin or alloy resin, which is difficult to use because it imparts extremely high flame retardancy to the resin and also reduces impact resistance in the past. Further, they have found a remarkable effect that good fluidity can be obtained. This makes it possible to obtain a molded product having excellent impact resistance, fluidity, and flame retardancy, and it is possible to produce a thin, large-sized and wide molded product.

[0009]

Means for Solving the Problems In the present invention, 100 parts by weight of a polycarbonate resin (A), an average composition formula (1) R ¹ _m R ² _n SiO _{(4-m−n) / 2} (1) ( In the formula, R ¹ represents a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 4, and R ² represents a monovalent aromatic hydrocarbon group having a carbon number of 6 to 24. R ¹ , R ² May be present in two or more types, and m and n represent numbers satisfying 1.1 ≦ m + n ≦ 1.7 and 0.4 ≦ n / m ≦ 2.5. Polyorganosiloxane-containing graft obtained by graft-polymerizing vinyl type monomer (c-2) in the presence of 0.1 to 20 parts by weight of silicone compound (B) and polyorganosiloxane particles (c-1). Copolymer (C)
The present invention relates to a flame-retardant resin composition containing 0.1 to 20 parts by weight.

The present invention will be described in detail below. In the present invention
Polycarbonate resin (A) used is
Carbonate, Polycarbonate / Polyethylene terephthalate
Rate mixed resin and polycarbonate / polybutylene
Polycarbonate / poly such as terephthalate mixed resin
Ester mixed resin, polycarbonate / acrylonitri
Lu-styrene copolymer mixed resin, polycarbonate / br
Tadiene rubber-styrene copolymer (HIPS resin) mixture
Resin, Polycarbonate / Acrylonitrile-Butadier
Rubber-styrene copolymer (ABS resin) mixed resin,
Polycarbonate / Acrylonitrile-Butadiene Rubber-
α-methylstyrene copolymer mixed resin, polycarbonate
/ Styrene-butadiene rubber-acrylonitrile-N
-Phenylmaleimide copolymer mixed resin, polycarbonate
/ Acrylonitrile-Acrylic rubber-Styrene copolymer
Combined (AAS resin) mixed resin and polycarbonate
Polycarbonate composed of a resin part and a polyorganosiloxane part
A nate-polyorganosiloxane copolymer or the like is used.
be able to. In addition, these optional resins should be further mixed.
You may use together. In addition, polycarbonate resin
Used in mixed resins containing
Is the viscosity average molecular weight of the polycarbonate in terms of molding processability?
, The upper limit is preferably 50,000, and 25,000
Is more preferable, and 19000 is further
preferable. The lower limit is preferably 10,000,
It is more preferably 15,000. This viscosity average molecule
The amount (Mv) was adjusted to 20 ° C using an Ubbelohde viscometer.
Measure the viscosity of the methylene chloride solution in the
The viscosity [η] is obtained and calculated by the following formula. [Η] = 1.23 × 10^-5Mv^0.83 In the case of mixed resin, the total amount of mixed resin
Polycarbonate is preferably 50% by weight or more, more preferably
60% by weight or more, more preferably 70% by weight
Occupy the above.

The polycarbonate is not particularly limited and various polycarbonates can be mentioned. Usually, an aromatic polycarbonate produced by reacting a dihydric phenol with a carbonate precursor can be used. That is, a product produced by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method, that is, a reaction of a dihydric phenol and phosgene, a transesterification method of a dihydric phenol and diphenyl carbonate, etc. is used. be able to.

As the dihydric phenol, various ones can be mentioned, but in particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] and bis (4
-Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4 '
-Dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, Bis (4-
Examples thereof include hydroxyphenyl) ether and bis (4-hydroxyphenyl) ketone. A particularly preferred dihydric phenol is a bis (hydroxyphenyl) alkane-based one, particularly bisphenol A as a main raw material. Further, the carbonate precursor is carbonyl halide, carbonyl ester, haloformate or the like, and specifically, phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate or the like.
In addition to these, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone,
You may mix and use 2 or more types. The polycarbonate may have a branched structure, and as the branching agent, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) is used. -1,3,5-triisopropylbenzene, phloroglysin, trimellitic acid, isatin bis (o-cresol), etc. In addition, for controlling the molecular weight, phenol, pt-butylphenol, pt- Octylphenol, p-cumylphenol and the like are used.

The silicone compound which is the component (B) of the present invention comprises an aromatic group-containing organosiloxane compound, and comprises a Q unit (SiO ₂ ), a T unit (RSiO _1.5 ),
D unit (R ₂ SiO) and M unit (R ₃ SiO _0.5 )
The average composition formula (1) R ¹ _m R ² _n SiO _{(4-m−n) / 2} (1) (wherein R ¹ is A monovalent aliphatic hydrocarbon group having a carbon number of 1 to 4 is represented, R ² represents a monovalent aromatic hydrocarbon group having a carbon number of 6 to 24. Two or more kinds of R ¹ and R ² are present. M and n represent a number satisfying 1.1 ≦ m + n ≦ 1.7 and 0.4 ≦ n / m ≦ 2.5).

The aromatic group-containing organosiloxane compound represented by the average composition formula (1) has 1 to 4 carbon atoms in the molecule.
Having both a monovalent aliphatic hydrocarbon group R ¹ and a monovalent aromatic hydrocarbon group R ² having 6 to 24 carbon atoms, and the molar ratio m + n of all the hydrocarbon groups and the number of Si atoms is 1.1
≦ m + n ≦ 1.7, carbon number is 1
~ 4 monovalent aliphatic hydrocarbon group R ¹ and 6 to 24 carbon atoms
The molar ratio n / m with the monovalent aromatic hydrocarbon group R ² is 0.
The condition of 4 ≦ n / m ≦ 2.5 is satisfied. The ratio of each element and each hydrocarbon group is hydrogen,
Calculated using NMR of carbon and silicon.

The aliphatic hydrocarbon group R ¹ having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, s-
Examples thereof include a butyl group and a t-butyl group. Of these, a methyl group and an ethyl group are preferable because of their excellent flame retarding effect, and a methyl group is more preferable. All of these plural R ¹ may be the same or different groups may be mixed. When the number of carbon atoms of the aliphatic hydrocarbon group is 5 or more, the flame retardancy of the aromatic group-containing organosiloxane compound itself is lowered, and thus the flame retarding effect is lowered.

The monovalent aromatic hydrocarbon group R ² having 6 to 24 carbon atoms is not particularly limited, and examples thereof include a phenyl group and
Examples thereof include a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a naphthyl group, an anthracenyl group and the like. Among these, an aromatic group having no substituent on the aromatic ring is preferable because of its excellent flame retarding effect, and a phenyl group is more preferable. These multiple R
All ² may be the same or different groups may be mixed.

The molar ratio m + of all hydrocarbon groups to the number of Si atoms
n is in the range of 1.1 ≦ m + n ≦ 1.7. m
The value of + n is preferably 1.15 ≦ m + n ≦ 1.65, more preferably 1.18 ≦ m + n ≦ 1.6, and further preferably 1.20 ≦ m + n ≦ 1.55. m + n
Whether the value of is less than 1.1 or greater than 1.7,
It is not preferable because the flame retarding effect of the aromatic group-containing organosiloxane compound decreases. The structure in the above range can be constructed by introducing T units and / or Q units into the skeleton of the organosiloxane compound, and generally, the larger the amount of these units introduced, the easier the above range is achieved. it can. The total introduction amount of T units and Q units is preferably 20 mol% or more in all Si atoms, and 25
More preferably, it is 30 mol% or more, and most preferably 30 mol% or more.

A monovalent aliphatic hydrocarbon group R ¹ having ¹ to 4 carbon atoms and a monovalent aromatic hydrocarbon group R ² having 6 to 24 carbon atoms
And the molar ratio n / m is within the range of 0.4 ≦ n / m ≦ 2.5. If n / m is less than 0.4, the number of monovalent aliphatic hydrocarbon groups R ¹ increases in the molecule, but at this time, the heat resistance of the aromatic group-containing organosiloxane compound decreases and the aromatic group-containing organosiloxane compound decreases. This causes a decrease in the flame retarding effect of the organosiloxane compound. On the other hand, if n / m is 2.5 or more, the flame retarding effect of the aromatic group-containing organosiloxane compound is reduced. The value of n / m is preferably 0.43 ≦ n / m ≦ 2.3, more preferably 0.4.
5 ≦ n / m ≦ 2.1, more preferably 0.47 ≦ n /
m ≦ 2.0.

Such an aromatic group-containing organosiloxane compound can be easily synthesized by a known silicone synthesis method. That is, a monofunctional silicon compound represented by R ₃ SiX, a difunctional silicon compound represented by R ₂ SiX ₂ , a trifunctional silicon compound represented by RSiX ₃ , a tetrahalogenated silicon, a tetraalkoxysilane, And a condensation reaction of at least one kind, preferably at least two kinds of silicon compounds selected from the organic silicon compounds, which are condensates thereof, and inorganic silicon compounds such as water glass and metal silicates as necessary. Can be synthesized by. In the formula, R represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group. X represents a group that can be condensed to form a siloxane bond, such as a halogen, a hydroxyl group or an alkoxyl group.

The reaction conditions vary depending on the substrate used and the composition and molecular weight of the target compound. The reaction can generally be carried out by mixing the silicon compound, optionally in the presence of water, an acid and / or an organic solvent while optionally heating. The use ratio of each silicon compound may be appropriately set in consideration of the content of each unit and the ratio of aromatic hydrocarbon groups to aliphatic hydrocarbon groups so that the obtained aromatic group-containing organosiloxane compound satisfies the above conditions. Good.

The addition amount of the silicone compound (B) in the present invention is 100% of the polycarbonate resin (A).
It is 0.1 to 20 parts by weight with respect to parts by weight. If the addition amount is less than 0.1 parts by weight, the flame retardancy may be insufficient, and if it is 20 parts by weight or more, the moldability of the resin composition tends to deteriorate. From the viewpoint of the balance of fluidity, flame retardancy and impact resistance, the upper limit of the addition amount of the silicone compound (B) is 15
Part by weight is preferable, and 10 parts by weight is more preferable. on the other hand,
The lower limit of the addition amount is preferably 0.3 part by weight, more preferably 0.5 part by weight.

When the polycarbonate resin (A) is a polycarbonate, the upper limit of the addition amount of the silicone compound (B) is preferably 8 parts by weight from the viewpoint of the balance of fluidity, flame retardancy and impact resistance. 5 parts by weight is more preferable, and 3 parts by weight is further preferable. On the other hand, the lower limit of the addition amount is preferably 0.5 part by weight, more preferably 0.8 part by weight, still more preferably 1 part by weight.

When the polycarbonate resin (A) is an alloy of polycarbonate and polyester, the upper limit of the addition amount of the silicone compound (B) is from the viewpoint of the balance of fluidity, flame retardancy and impact resistance. 15 parts by weight is preferable, 10 parts by weight is more preferable, 5 parts by weight is further preferable, and 3 parts by weight is particularly preferable. On the other hand, the lower limit of the addition amount is preferably 0.5 part by weight, more preferably 0.8 part by weight, still more preferably 1 part by weight.

When the polycarbonate resin (A) is an alloy of polycarbonate and polystyrene, the upper limit of the addition amount of the silicone compound (B) is from the viewpoint of the balance of fluidity, flame retardancy and impact resistance. 15 parts by weight is preferable and 10 parts by weight is more preferable. On the other hand, the lower limit of the addition amount is preferably 0.5 part by weight, more preferably 1 part by weight.

The polyorganosiloxane-containing graft copolymer (C) of the present invention comprises polyorganosiloxane particles (c).
It is obtained by graft-polymerizing the vinyl monomer (c-2) in the presence of -1).

The polyorganosiloxane particles (c-1) used in the polyorganosiloxane-containing graft copolymer (C) can be obtained by light scattering method or electron microscope observation from the viewpoint of flame retardancy. The average particle size is 0.
008-0.6μm, and further 0.008-0.2μ
m, more preferably 0.01 to 0.15 μm, especially 0.
It is preferably from 01 to 0.1 μm. It tends to be difficult to obtain those having an average particle size of less than 0.008 μm, and when it exceeds 0.6 μm, the flame retardancy tends to deteriorate. Coefficient of variation of particle size distribution of the polyorganosiloxane particles (100 × standard deviation / average particle size (%))
Is preferably 10 to 70%, more preferably 20 to 60%, particularly preferably 20 to 5 from the viewpoint that the appearance of the molded article surface of the resin composition containing the flame retardant of the present invention is good.
It is desirable to control it to 0%.

The polyorganosiloxane particles (c-1) used in the present invention are not only particles composed of only polyorganosiloxane but also modified polyorganosiloxane containing 5% or less of another (co) polymer. It is a concept that includes. That is, the polyorganosiloxane particles may contain, for example, 5% or less of polybutyl acrylate, butyl acrylate-styrene copolymer and the like in the particles.

The polyorganosiloxane particles (c-
Specific examples of 1) include polydimethylsiloxane particles,
Examples thereof include polymethylphenylsiloxane particles and dimethylsiloxane-diphenylsiloxane copolymer particles. These may be used alone or in combination of two or more.

The polyorganosiloxane particles (c-
1) is, for example, an organosiloxane and / or a bifunctional silane compound, a vinyl-based polymerizable group-containing silane compound,
It can be obtained by polymerizing a polyorganosiloxane-forming component composed of a trifunctional or higher functional silane compound or the like, which is used as necessary.

The organosiloxane and / or the bifunctional silane compound is a component constituting the main skeleton of the polyorganosiloxane chain, and specific examples of the organosiloxane include hexamethylcyclotrisiloxane (D
3), octamethylcyclotetrasiloxane (D4),
Specific examples of difunctional silane compounds such as decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), and hexadecamethylcyclooctasiloxane (D8) are diamine. Ethoxydimethylsilane, dimethoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, trifluoropropylmethyldimethoxysilane, Examples include octadecylmethyldimethoxysilane. Among these, 70 to 100%, and further 80 to 80% of D4 or the mixture of D3 to D7 or the mixture of D3 to D8 from the viewpoint of economical efficiency and flame retardancy.
Contains 100% and the remaining components are 0 to 3 such as diphenyldimethoxysilane and diphenyldiethoxysilane.
Those containing 0%, more preferably 0 to 20% are preferably used.

The vinyl-based polymerizable group-containing silane compound is an organosiloxane, a bifunctional silane compound, or a trifunctional silane compound.
It is a component for copolymerizing with a functional silane compound or the like to introduce a vinyl-based polymerizable group into the side chain or terminal of the copolymer. The vinyl-based polymerizable group is a vinyl-based monomer (c -2) acts as a graft active site when chemically bonding to the vinyl-based (co) polymer formed from. Furthermore, it is a component that can be used as a cross-linking agent by radically reacting between graft active points with a radical polymerization initiator to form a cross-linking bond. At this time, the same radical polymerization initiator as that which can be used in the below-mentioned graft polymerization can be used. Even when crosslinking is carried out by a radical reaction, some of them remain as grafting active points, so that grafting is possible.

Specific examples of the vinyl-based polymerizable group-containing silane compound include, for example, general formula (I):

[0033]

[Chemical 1]

(In the formula, R ⁴ is a hydrogen atom, a methyl group, or R ⁵
Is a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is 1 to 6 carbon atoms
An alkoxyl group, o is 0, 1 or 2, and p is a number of 1 to 6), a silane compound represented by the general formula (I
I):

[0035]

[Chemical 2]

(In the formula, R ⁵ , Y, o and p are represented by the general formula (I)
A silane compound represented by the general formula (II
I):

[0037]

[Chemical 3]

(Wherein R ⁵ , Y and o are the same as those in the general formula (I)), the general formula (IV):

[0039]

[Chemical 4]

(Wherein R ⁵ , Y and o are the same as those in the general formula (I), R ⁶ represents a divalent hydrocarbon group having 1 to ⁶ carbon atoms), a general formula (V ):

[0041]

[Chemical 5]

(In the formula, R ⁵ , Y and o are the same as those in the general formula (I), and R ⁷ is a divalent hydrocarbon group having 1 to 18 carbon atoms)
Examples include silane compounds represented by. Specific examples of R ^{5 in} the general formulas (I) to (V) include an alkyl group such as a methyl group, an ethyl group and a propyl group, a phenyl group, and the like, and a specific example of Y includes, for example, methoxy. Group, an ethoxy group, a propoxy group, a butoxy group, and other alkoxy groups having 1 to 6 carbon atoms. Further, specific examples of R ^{6 in} the general formula (IV) include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group, and specific examples of R ⁷ in the general formula (V) include a methylene group, Examples thereof include ethylene group, trimethylene group and tetramethylene group.

Specific examples of the silane compound represented by the general formula (I) include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane and γ-methacryloyl. Oxypropyldimethylmethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyldiethoxymethylsilane,
γ-methacryloyloxypropyltripropoxysilane, γ-methacryloyloxypropyldipropoxymethylsilane, γ-acryloyloxypropyldimethoxymethylsilane, γ-acryloyloxypropyltrimethoxysilane and the like are among the silane compounds represented by the general formula (II). As specific examples, p-vinylphenyldimethoxymethylsilane, p-vinylphenyltrimethoxysilane, p-vinylphenyltriethoxysilane, p-
Specific examples of the silane compound represented by the general formula (III) include vinylphenyldiethoxymethylsilane and the like, for example, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and the like. Specific examples of the silane compound represented by the formula (IV) include allylmethyldimethoxysilane, allylmethyldiethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane, and specific examples of the silane compound represented by the general formula (V). Examples include mercaptopropyltrimethoxysilane and mercaptopropyldimethoxymethylsilane. Among these, general formula (I) and general formula (II
I) and the silane compound represented by the general formula (V) are preferably used in terms of economy.

When the vinyl-based polymerizable group-containing silane compound is a trialkoxysilane type, it also functions as a trifunctional or higher-functional silane compound shown below.

The trifunctional or higher functional silane compound is copolymerized with the organosiloxane, the bifunctional silane compound, the vinyl-based polymerizable group-containing silane compound or the like to introduce a crosslinked structure into the polyorganosiloxane to impart rubber elasticity. It is used as a cross-linking agent for polyorganosiloxane. Specific examples include tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, octadecyl. Examples thereof include trifunctional and trifunctional alkoxysilane compounds such as trimethoxysilane. Among these, tetraethoxysilane and methyltriethoxysilane are preferably used from the viewpoint of high crosslinking efficiency.

The ratio of the organosiloxane, the bifunctional silane compound, the vinyl-based polymerizable group-containing silane compound, and the trifunctional or higher functional silane compound used during the polymerization is usually an organosiloxane and / or a bifunctional silane compound (organosiloxane). The ratio of the difunctional silane compound to the bifunctional silane compound is usually 100/0 to 0/100, further 1
00/0 to 70/30) 50 to 99.9%, and further 6
0 to 99%, vinyl polymerizable group-containing silane compound 0 to 4
It is preferably 0%, more preferably 0.5 to 30%, and a trifunctional or higher functional silane compound 0 to 50%, further preferably 0.5 to 39%. Incidentally, vinyl-based polymerizable group-containing silane compounds, 3
Functional silane compounds do not become 0% at the same time, and it is preferable to use 0.1% or more of any of them.

When the use ratio of the above-mentioned organosiloxane and bifunctional silane compound is too small,
The resin composition obtained by blending tends to be brittle. On the other hand, when the amount is too large, the amounts of the vinyl-based polymerizable group-containing silane compound and the trifunctional or higher functional silane compound are too small, and the effect of using these tends to be difficult to be exhibited. Further, when the ratio of the vinyl-based polymerizable group-containing silane compound or the trifunctional or higher-functional silane compound is too small, the flame retardancy-producing effect is low, and when the ratio is too large, it is blended. The resin composition thus obtained tends to become brittle.

The polyorganosiloxane particles (c-
1) is, for example, emulsion-polymerized with a polyorganosiloxane-forming component consisting of the above-mentioned organosiloxane and / or a bifunctional silane compound, a vinyl-based polymerizable group-containing silane compound, and a trifunctional or more functional silane compound used as necessary. Therefore, it is preferable to manufacture it.

The emulsion polymerization can be carried out, for example, by emulsifying and dispersing the polyorganosiloxane-forming component and water in the presence of an emulsifier in water by mechanical shearing to bring the mixture into an acidic state. In this case, when emulsified droplets of several μm or more are prepared by mechanical shearing, the average particle size of the polyorganosiloxane particles obtained after polymerization is controlled within the range of 0.02 to 0.6 μm depending on the amount of the emulsifier used. be able to. The coefficient of variation of the obtained particle size distribution (100 x standard deviation / average particle size (%)) is 20 to 70.
% Can be obtained.

When polyorganosiloxane particles having a particle size distribution of 0.1 μm or less and a narrow particle size distribution are produced, it is preferable to carry out polymerization in multiple stages. For example, 1 to 20% of an emulsion consisting of emulsified droplets of several μm or more obtained by emulsifying the polyorganosiloxane-forming component, water and an emulsifier by mechanical shearing is first obtained by emulsion polymerization in an acidic state. Using the polyorganosiloxane particles as seeds, the remaining emulsion is added and polymerized in the presence thereof. The polyorganosiloxane particles thus obtained have an average particle size of 0.02 to 0.1 μm depending on the amount of the emulsifier,
Moreover, the variation coefficient of the particle size distribution can be controlled to 10 to 60%. In a more preferred method, in the multistage polymerization, a vinyl-based monomer (for example, styrene, butyl acrylate, methyl methacrylate, etc.) used in the below-described graft polymerization is used in place of the seed of the polyorganosiloxane particles in a usual emulsion polymerization method. When the same multi-stage polymerization is carried out using the vinyl-based (co) polymer obtained by (co) polymerizing by (1), the average particle size of the obtained polyorganosiloxane (modified polyorganosiloxane) particles is 0.008 to
0.1 μm and coefficient of variation of particle size distribution is 10-50%
Can be controlled. The emulsified droplets of several μm or more can be prepared by using a high-speed stirrer such as a homomixer.

In the emulsion polymerization, an emulsifier that does not lose its emulsifying ability under acidic conditions is used. Specific examples include alkylbenzene sulfonic acid, sodium alkylbenzene sulfonate, alkyl sulfonic acid, sodium alkyl sulfonate, sodium (di) alkyl sulfosuccinate,
Examples thereof include sodium polyoxyethylene nonylphenyl ether sulfonate, sodium alkylsulfate and the like. These may be used alone or in combination of two or more. Among these, alkylbenzene sulfonic acid, sodium alkylbenzene sulfonate, alkyl sulfonic acid, sodium alkyl sulfonate,
Sodium (di) alkylsulfosuccinate is preferable because the emulsion stability of the emulsion is relatively high. Furthermore, alkylbenzenesulfonic acid and alkylsulfonic acid are particularly preferable because they also act as a polymerization catalyst for the polyorganosiloxane-forming component.

In the acidic state, the system may be an inorganic acid such as sulfuric acid or hydrochloric acid, an alkylbenzenesulfonic acid, an alkylsulfonic acid,
It is obtained by adding an organic acid such as trifluoroacetic acid, and the pH is preferably adjusted to 1 to 3 in terms of not corroding the production facility and obtaining an appropriate polymerization rate, and further 1.0 to 2 It is more preferable to adjust to 0.5.

The heating for polymerization is preferably 60 to 120 ° C., and 70 to 10 from the viewpoint of obtaining an appropriate polymerization rate.
0 ° C is more preferable.

Under acidic conditions, the Si--O--Si bond forming the skeleton of the polyorganosiloxane is in an equilibrium state of cleavage and formation, and this equilibrium changes with temperature, so the stability of the polyorganosiloxane chain is stable. For
It is preferable to neutralize by adding an aqueous alkaline solution such as sodium hydroxide, potassium hydroxide or sodium carbonate. Furthermore, in the equilibrium, a higher molecular weight or a higher degree of crosslinking is more likely to be generated on the production side as the temperature becomes lower.
It is preferable that the polyorganosiloxane-forming component is polymerized at 60 ° C. or higher, then cooled to room temperature or lower and held for 5 to 100 hours, and then neutralized.

The polyorganosiloxane particles thus obtained are, for example, organosiloxane and / or 2
When formed from a functional silane compound and a vinyl-based polymerizable group-containing silane compound, they are usually copolymerized randomly to form a polymer having a vinyl-based polymerizable group. Further, when a trifunctional or higher functional silane compound is copolymerized, it has a crosslinked network structure. Furthermore, when the vinyl-based polymerizable groups are crosslinked by a radical reaction with a radical polymerization initiator as used in the below-mentioned graft polymerization, it has a crosslinked structure in which vinyl-based polymerizable groups are chemically bonded, and The unreacted vinyl polymerizable group remains. Toluene insoluble amount of the polyorganosiloxane particles (0.5 g of the particles was added to 80 ml of toluene at room temperature for 24 hours).
From the viewpoint of the flame retardant effect, the toluene insoluble content after immersion for a period of time is 95% or less, more preferably 90% or less.

By graft-polymerizing the vinyl-based monomer (c-2) on the polyorganosiloxane particles obtained by the above process, a polyorganosiloxane-containing graft copolymer can be obtained.

The polyorganosiloxane-containing graft copolymer has a structure in which the vinyl-based monomer (c-2) is grafted onto the polyorganosiloxane particles.
The graft ratio is 5 to 150%, and further 15 to 120
% Is preferable from the viewpoint of good balance between flame retardancy and impact resistance.

The vinyl-based monomer (c-2) is a component used to obtain a flame retardant composed of a polyorganosiloxane-containing graft copolymer. When blended with the resin (A), it is used to ensure compatibility between the graft copolymer and the polycarbonate resin (A) and to uniformly disperse the flame retardancy and impact resistance in the polycarbonate resin. It is also an ingredient. Therefore, the vinyl-based monomer (c-2)
The solubility parameter of the polymer of the vinyl monomer is 9.15 to 10.15 ((cal / cm ³ ).
^(1/2 , hereinafter, unit omitted), and 9.17-
It is preferably chosen to be 10.10, especially 9.20 to 10.05. If the solubility parameter deviates from the above range, the flame retardancy tends to decrease.

The solubility parameter is John
"Polymer Handbook" published by Wiley & Son, Inc. 1
1999, 4th edition, section VII, 682-685.
The values are calculated by using the group parameter of Small by the group contribution method described in page). For example, polymethylmethacrylate (repeating unit molecular weight 100 g / mo
l, density = 1.19 g / cm ³ (hereinafter, unit omitted) 9.25, polybutyl acrylate (same 128,
1.06) 8.97, polybutylmethacrylate (142, 1.06) 9.47, polystyrene (104, 1.05) 9.03, polyacrylonitrile (53, 1.18) ) 12.71. The density of each polymer is shown in "Ullmann's Encyclopedia of Industrial Chemistry"(ULLMANN'S ENCYCLO) published by VCH.
PEDIA OF INDUSTRIAL CHEMI
STRY) ", 1992, Volume A21, page 169. In addition, the solubility parameter δ of the copolymer
For c, the value of the main component is used when the weight fraction is less than 5%, and the additivity is established by the weight fraction when the weight fraction is 5% or more. That is, it can be calculated by the formula (1) from the solubility parameter δn of the homopolymer of each vinyl monomer constituting the copolymer composed of m kinds of vinyl monomers and the weight fraction Wn thereof.

[0060]

[Equation 1]

For example, the solubility parameter of a copolymer consisting of 75% styrene and 25% acrylonitrile is
Substituting into the equation (1) using the solubility parameter of polystyrene 9.03 and the solubility parameter of polyacrylonitrile 12.71 gives a value of 9.95.

The solubility parameter δs of the vinyl polymer obtained by polymerizing the vinyl monomer in two or more steps and changing the type of the vinyl monomer in each step.
Is the value obtained by dividing the total weight of the finally obtained vinyl-based polymer by the weight of the vinyl-based polymer obtained in each stage, that is, the weight fraction, and the additivity is established. That is, it can be calculated by the equation (2) from the solubility parameter δi of the polymer obtained in each stage and the weight fraction Wi thereof, which is obtained by polymerizing in q stages.

[0063]

[Equation 2]

For example, assume that 50 parts of a copolymer consisting of 75% styrene and 25% acrylonitrile is obtained in the first stage and 50 parts of a polymer of methyl methacrylate is obtained in the second stage. , The solubility parameter of the polymer obtained by this two-step polymerization is styrene (75
%)-Acrylonitrile (25%) copolymer solubility parameter of 9.95 and polymethylmethacrylate solubility parameter of 9.25, and substituting into equation (2).
A value of 60 is obtained.

The amount of the vinyl-based monomer (c-2) used is 40 to 90 of the polyorganosiloxane particles (c-1).
%, Further 50 to 80%, especially 50 to 75%, so that the total amount is 100%, it is 60 to 10%, further 50 to 20%, and especially 50 to 25%. preferable. If the amount of the vinyl-based monomer (c-2) used is too large or too small, the flame retardancy tends not to be sufficiently exhibited.

As the vinyl-based monomer (c-2),
For example, aromatic vinyl monomers such as styrene, α-methylstyrene, paramethylstyrene, parabutylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, acrylic acid. Propyl, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxy methacrylate Examples thereof include (meth) acrylic acid ester-based monomers such as ethyl, carboxyl group-containing vinyl-based monomers such as itaconic acid, (meth) acrylic acid, fumaric acid and maleic acid. As described above, these may be used alone or in combination of two or more as long as the solubility parameter of the polymer falls within the range described above.

As the graft polymerization, a usual seed emulsion polymerization can be applied, and the polyorganosiloxane particles (c-1)
Radical polymerization of the vinyl monomer (c-2) may be carried out in the latex. In addition, vinyl-based monomers (c-
2) may be polymerized in one step or in two or more steps.

The radical polymerization may be carried out by a method in which the reaction is proceeded by thermally decomposing a radical polymerization initiator, or a reaction in a redox system using a reducing agent without any particular limitation.

Specific examples of the radical polymerization initiator include cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, di-t-butylperoxide and t-butylperoxy. Organic peroxides such as laurate, lauroyl peroxide, succinic acid peroxide, cyclohexane nonoxide, acetylacetone peroxide, inorganic peroxides such as potassium persulfate and ammonium persulfate, 2,2′-azobisisobutyro Nitrile, 2,2'-azobis-2,4-
Examples thereof include azo compounds such as dimethylvaleronitrile. Among these, organic peroxides or inorganic peroxides are particularly preferable because of their high reactivity.

As the reducing agent used in the redox system, ferrous sulfate / glucose / sodium pyrophosphate, ferrous sulfate / dextrose / sodium pyrophosphate, or ferrous sulfate / sodium formaldehyde sulfoxylate / Examples include a mixture of ethylenediamine acetate and the like.

The amount of the radical polymerization initiator used is usually 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the polyorganosiloxane particles (c-1) used. And especially 0.03 to 5
It is preferably part by weight. When the amount of the radical polymerization initiator is less than 0.005 parts by weight, the reaction rate is low,
The production efficiency tends to be poor, and if it exceeds 20 parts by weight, heat generation during the reaction tends to be large and production tends to be difficult.

Further, a chain transfer agent can be used if necessary in radical polymerization. The chain transfer agent is not particularly limited as long as it is used in ordinary emulsion polymerization. Specific examples of the chain transfer agent include t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, and n-hexyl mercaptan.

The chain transfer agent is an optional component, but when used, it is preferably used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the vinyl monomer (c-2).
If the amount of the chain transfer agent is less than 0.01 parts by weight, the effect used cannot be obtained, and if it exceeds 5 parts by weight, the polymerization rate tends to be slow and the production efficiency tends to be low. Further, the reaction temperature during the polymerization is usually preferably 30 to 120 ° C.

In the above-mentioned polymerization, when the polyorganosiloxane particles (c-1) contain a vinyl-based polymerizable group, when the vinyl-based monomer (c-2) is polymerized by the radical polymerization initiator, Organosiloxane particles (c-1)
A graft is formed by reacting with the vinyl-based polymerizable group. When the polyorganosiloxane particles (c-1) do not have a vinyl polymerizable group, when a specific radical initiator such as t-butylperoxylaurate is used, the organic group such as a methyl group bonded to a silicon atom can be converted. Hydrogen is extracted, and the vinyl radicals (c-2) are polymerized by the generated radicals to form a graft.

Further, 0.1 to 10%, preferably 0.5 to 5% of the vinyl-based monomer (c-2) is polymerized using a vinyl-based polymerizable group-containing silane compound, and the pH is 5 or less. Grafts are formed even when the redistribution reaction is carried out under the acidic condition of.
This is because the Si-O-Si bond of the main skeleton of the polyorganosiloxane is in an equilibrium state of cleavage and formation in an acidic state, and therefore, in this equilibrium state, the vinyl monomer and the vinyl polymerizable group-containing silane compound are When copolymerized, the side chain silane of the vinyl-based copolymer being produced or produced by the polymerization reacts with the polyorganosiloxane chain to produce a graft. The vinyl-based polymerizable group-containing silane compound,
If necessary, it may be the same as the one used in the production of the polyorganosiloxane particles (c-1). When the amount of the vinyl-based polymerizable group-containing silane compound is less than 0.1%, the vinyl-based monosilane is used. When the proportion of the monomer (c-2) to be grafted is reduced and exceeds 10%, the stability of the latex tends to be low.

In the polymerization of the vinyl-based monomer (c-2) in the presence of the polyorganosiloxane particles, the portion corresponding to the branch of the graft copolymer (here, the vinyl-based monomer (c-2) is used. Polymer) is not by-grafted on the trunk component (here, polyorganosiloxane particles (c-1)) but is polymerized alone by the branch component alone, so-called free polymer is obtained as a by-product, which is free from the graft copolymer. Although it is obtained as a mixture of polymers, both are collectively referred to as a graft copolymer in the present invention.

The graft copolymer obtained by emulsion polymerization may be used as it is as a latex, but it is preferable to use it as a powder by separating the polymer from the latex because of its wide application range. As a method for separating the polymer, a usual method, for example, coagulation and separation of the latex by adding a metal salt such as calcium chloride, magnesium chloride or magnesium sulfate to the latex,
Examples of the method include washing with water, dehydration, and drying. Also, a spray drying method can be used.

The amount of the polyorganosiloxane-containing graft copolymer (C) added in the present invention is 0.1 to 2 with respect to 100 parts by weight of the polycarbonate resin (A).
0 parts by weight. If the addition amount is less than 0.1 parts by weight, flame retardancy and impact resistance may be insufficient, and if it is 20 parts by weight or more, the fluidity of the resin composition tends to decrease. From the viewpoint of the balance among fluidity, flame retardancy and impact resistance, the upper limit of the amount of the polyorganosiloxane-containing graft copolymer (C) added is preferably 15 parts by weight, more preferably 10 parts by weight. The lower limit of the addition amount is preferably 0.3 part by weight,
0.5 parts by weight is more preferable. The total amount with the component (B) is preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight.

When the polycarbonate resin (A) is a polycarbonate, the upper limit of the amount of the polyorganosiloxane-containing graft copolymer (C) added is from the viewpoint of the balance of fluidity, flame retardancy and impact resistance. , 8 parts by weight is preferred, 5 parts by weight is more preferred, and 3 parts by weight is even more preferred. On the other hand, the lower limit of the addition amount is preferably 0.3 part by weight, more preferably 0.5 part by weight, further preferably 0.8 part by weight, and particularly preferably 1 part by weight. The total amount with the component (B) is particularly preferably 1 to 6 parts by weight.

When the polycarbonate resin (A) is an alloy of polycarbonate and polyester, the upper limit of the addition amount of the polyorganosiloxane-containing graft copolymer (C) is fluidity, flame retardancy and impact resistance. From the viewpoint of the balance of 10 parts by weight, 10 parts by weight is preferable, 8 parts by weight is more preferable, and 6 parts by weight is further preferable. On the other hand, the lower limit of the addition amount is preferably 0.5 part by weight, more preferably 0.8 part by weight, further preferably 1 part by weight, particularly preferably 2 parts by weight. The total amount with the component (B) is particularly preferably 1 to 6 parts by weight.

When the polycarbonate resin (A) is an alloy of polycarbonate and polystyrene, the upper limit of the addition amount of the polyorganosiloxane-containing graft copolymer (C) is fluidity, flame retardancy and impact resistance. From the viewpoint of the balance of, 15 parts by weight is preferable, and 10 parts by weight is preferable. On the other hand, the lower limit of the addition amount is preferably 0.5 parts by weight,
1 part by weight is more preferred. The total amount with the component (B) is 2 to
20 parts by weight are particularly preferred.

Examples of the organic alkali metal salt and / or organic alkaline earth metal salt (D) used in the present invention include aromatic sulfonamide metal salts, aromatic sulfonic acid metal salts, and perfluoroalkanes. Examples thereof include metal salts of sulfonic acid. As the metal salt of aromatic sulfonamide, the following general formula (VI):

[0083]

[Chemical 6]

(Wherein R ⁸ and R ⁹ are the same or different and each represents a monovalent aromatic group, and M ⁺ represents a metal cation) or the general formula (VII):

[0085]

[Chemical 7]

(In the formula, R ¹⁰ represents a monovalent aromatic group,
R ¹¹ represents a monovalent organic group containing sulfonyl or carbonyl, and M ⁺ represents a metal cation. However, R ¹⁰ and R ¹¹ may be bonded. ) Are preferred, and as the metal salt of aromatic sulfonic acid, the following general formula (VIII):

[0087]

[Chemical 8]

(In the formula, R ¹² and R ¹³ are the same or different and each represents a monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic group. Z is SO ₃ M represents a group (M is a metal cation), q represents an integer of 0 to 2, and two r are the same or different and represent an integer of 0 to 6, but 2
Except when two are 0 at the same time. Those shown in () are preferable.

As the metal salt of aromatic sulfonamide,
For example, a metal salt of saccharin, a metal salt of N- (p-tolylsulfonyl) -p-toluenesulfoimide, N-
Examples thereof include a metal salt of (N′-benzylaminocarbonyl) sulfanylimide and a metal salt of N- (phenylcarboxyl) -sulfanylimide.

As the metal salt of aromatic sulfonic acid, for example, a metal salt of diphenylsulfone-3-sulfonic acid, a metal salt of diphenylsulfone-3,3'-disulfonic acid, diphenylsulfone-3,4'- Examples include metal salts of disulfonic acid.

The metal for forming the above metal salt is not particularly limited, and examples thereof include Group I metals (alkali metals) such as sodium and potassium, Group II metals, copper and aluminum. Alkali metals are preferred.

Among these, particularly, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfoimide, potassium salt of N- (N'-benzylaminocarbonyl) sulfanylimide and diphenylsulfone-3-.
The potassium salt of sulfonic acid is preferred. More preferably,
N- (p-tolylsulfonyl) -p-toluenesulfoimide potassium salt and N- (N'-benzylaminocarbonyl) sulfanylimide potassium salt.

Examples of the metal salt of perfluoroalkanesulfonic acid include the following general formula (IX) CF ₃ (CF ₂ ) _s SO ₃ M (IX) (wherein M represents a metal cation and s represents 0 to 7). Which represents an integer of 1.) is preferable.

Preferred metal salts of perfluoroalkanesulfonic acid are those having 1 to 8 carbon atoms, and specifically, metal salts of perfluoromethanesulfonic acid, metal salts of perfluoroethanesulfonic acid, and perfluoropropanesulfone. Metal salt of acid, metal salt of perfluorobutane sulfonic acid, metal salt of perfluoromethyl butane sulfonic acid, metal salt of perfluorohexane sulfonic acid, metal salt of perfluoroheptane sulfonic acid, metal salt of perfluorooctane sulfonic acid And so on.

The metal for forming the metal salt of perfluoroalkanesulfonic acid is not particularly limited, and examples thereof include Group I metals (alkali metals) such as sodium and potassium, Group II metals, copper, aluminum and the like. Named
Alkali metals are particularly preferred. Among these, especially
A potassium salt of perfluorobutane sulfonic acid is preferably used. These organic alkali metal salts and / or organic alkaline earth metal salts may be used alone or in combination of two or more.

The blending amount of the organic alkali metal salt and / or the organic alkaline earth metal salt is preferably 0.01 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin (A). If the amount is less than 0.01 parts by weight, it may be difficult to obtain a remarkable flame retardant effect.
If the amount is more than parts by weight, the thermal stability during injection molding may be poor, and as a result, the moldability and impact resistance may be adversely affected. The range is more preferably 0.02 parts by weight or more and 2 parts by weight or less, and further preferably 0.03 parts by weight or more and 0.4 parts by weight or less. Particularly in this range, the balance of flame retardancy, moldability and impact resistance is further improved.

Further, to the flame-retardant resin composition of the present invention, in order to further enhance the flame retardancy, a fluorine-based resin can be added within a range not impairing the characteristics of the present invention. The fluororesin is a resin having a fluorine atom in the resin. Specific examples include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymer. In addition, if necessary, it is obtained by polymerizing a monomer used in the production of the fluororesin with a copolymerizable monomer in combination, as long as the physical properties such as flame retardancy of the obtained molded product are not impaired. You may use the obtained copolymer. These fluororesins may be used alone or in combination of two or more.

The molecular weight of the fluororesin is 1 to 20,000,000.
1,000,000 is preferable, and 2,000,000-100 is more preferable.
It is 0,000. Regarding the method for producing these fluororesins, they can be obtained by a generally known method such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization and the like.

The addition amount of the fluorine-based resin is not limited as long as the characteristics of the present invention are not impaired, but is preferably 0.01 to 5 parts by weight, more preferably 100 parts by weight of the polycarbonate-based resin (A). 0.02 to 3 parts by weight, particularly preferably 0.05 to 2 parts by weight. Addition amount is 0.
When it is less than 01, the effect of improving flame retardancy is small, and when it exceeds 5 parts by weight, moldability and the like are deteriorated, which is not preferable.

Further, the flame-retardant resin composition of the present invention may be combined with a reinforcing filler to form a reinforcing material. By adding a reinforcing filler, heat resistance, mechanical strength and the like can be further improved. Specific examples of the reinforcing filler include, for example, glass fiber, carbon fiber, potassium titanate fiber, fibrous filler such as glass beads, glass flakes, talc, mica, kaolin, wollastonite, smectite, diatomaceous earth, and carbonic acid. Examples thereof include calcium, calcium sulfate and barium sulfate. Particularly preferred as reinforcing fillers are silicate compounds and / or fibrous reinforcing agents.

The silicate compound has a chemical composition of S
A compound having a powdery, granular, acicular, plate-like shape containing an iO ₂ unit, such as talc, mica, magnesium silicate, aluminum silicate, calcium silicate, wollastonite, kaolin, diatomaceous earth, smectite And the like, which may be natural or synthetic. Of these, talc, mica and smectite are preferable. The average diameter of the silicate compound [particle diameter when converted to a circle obtained by image-processing a micrograph] is not particularly limited, but a preferable average diameter is 0.01
To 100 μm, and more preferably 0.1 to 50 μm.
μm, and more preferably 0.3 to 40 μm. If the average particle size is less than 0.01 μm, the strength improving effect is not sufficient, and if it exceeds 100 μm, the toughness tends to decrease.

Further, the silicate compound may be treated with a surface treating agent such as a silane coupling agent or a titanate coupling agent. Examples of the silane coupling agent include epoxy type silane, amino type silane, vinyl type silane and the like, and examples of the titanate type coupling agent include monoalkoxy type, chelate type, coordinate type and the like.

The method for treating the silicate compound with the surface treating agent is not particularly limited, and may be a usual method. For example, it can be carried out by adding the surface treating agent to the layered silicate and stirring or mixing in a solution or while heating.

Examples of the fibrous reinforcing agent include glass fiber and carbon fiber. When using the fibrous reinforcing agent, it is preferable to use chopped strand glass fibers treated with a sizing agent from the viewpoint of workability. Further, in order to enhance the adhesiveness between the resin and the fibrous reinforcing agent, it is preferable that the surface of the fibrous reinforcing agent is treated with a coupling agent, and a binder may be used. Examples of the coupling agent include the same compounds as described above.

When glass fiber is used as the reinforcing filler,
It is preferable that the diameter is 1 to 20 μm and the length is about 0.01 to 50 mm. If the fiber length is too short, the reinforcing effect is not sufficient, and conversely, if the fiber length is too long, the surface properties, extrusion processability, and moldability of the molded product deteriorate, which is not preferable.

The reinforcing filler may be used alone or in combination of two or more. When two or more kinds are mixed and used, there is no particular limitation, but a preferable combination is selected from kaolin, smectite and glass fiber.
One or more reinforcing fillers.

The addition amount of the reinforcing filler is not limited as long as it does not impair the characteristics of the present invention, but is preferably 0.5 to 100 parts by weight, more preferably 100 parts by weight of the polycarbonate resin (A). , 1 to 60 parts by weight, especially 2
-40 parts by weight is preferred. If the addition amount is less than 0.5 parts by weight, the effect of improving the mechanical strength is small, and if it exceeds 100 parts by weight, properties such as workability and impact resistance tend to be impaired.

The flame-retardant resin composition of the present invention includes any other thermoplastic or thermosetting resin within the range not impairing the present invention, such as liquid crystal polyester resin, polyester ester elastomer resin and polyester ether. Elastomer resin, polyolefin resin, polyamide resin, polystyrene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin, polysulfone resin, etc. may be added singly or in combination of two or more.

Further, in order to make the flame-retardant resin composition of the present invention have a higher performance, it is possible to use a heat stabilizer such as an antioxidant such as a phenol-based antioxidant, a thioether-based antioxidant, or a phosphorus-based stabilizer. It is preferable to use one or more agents together. Further, if necessary, usually well known, lubricants, mold release agents, plasticizers, flame retardants other than phosphorus, flame retardant aids such as zinc borate, ultraviolet absorbers, light stabilizers, pigments,
Dye, antistatic agent, conductivity imparting agent, dispersant, compatibilizer,
One or more kinds of additives such as antibacterial agents can be used in combination.

The method for producing the composition of the present invention is not particularly limited. For example, the above components and other additives, resins, etc. may be dried, if necessary, and then melt-kneaded in a melt-kneader such as a single-screw or twin-screw extruder. . When the compounding agent is a liquid,
It can also be manufactured by adding it to a twin-screw extruder halfway using a liquid supply pump or the like.

The method of molding the flame-retardant resin composition of the present invention is not particularly limited, and molding methods generally used for polycarbonate resins such as injection molding, blow molding, extrusion molding, vacuum molding, Press molding, calender molding, foam molding, etc. can be applied.

The flame-retardant resin composition of the present invention is suitable for various uses. Preferred applications include home appliances and O
Examples include injection-molded products such as equipment A parts, automobile parts, blow-molded products, extrusion-molded products, and foam-molded products.

[0113]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In the following, "parts" means parts by weight and "%" means% by weight unless otherwise specified.

The following method was used for analyzing the silicone compound (B). [Average compositional formula] The sample was dissolved in a solvent deuterated chloroform, and each ratio was calculated by NMR of hydrogen, carbon, and silicon.

Further, the structure of the polyorganosiloxane graft copolymer (C) was analyzed by the following method. [Polymerization conversion rate] Latex was dried in a hot air dryer at 120 ° C to 1
After drying for an hour, the solid component amount was obtained and calculated by 100 × solid component amount / charged monomer amount (%).

[Toluene-insoluble content] Solid of polyorganosiloxane particles obtained by drying the latex from 0.
Immerse 5 g in 80 ml of toluene at room temperature for 24 hours, and
Centrifugation was performed at 2000 rpm for 60 minutes to measure the weight fraction (%) of the toluene-insoluble portion of the polyorganosiloxane particles.

[Grafting Rate] 1 g of the graft copolymer was immersed in 80 ml of acetone at room temperature for 48 hours, and then 12000.
The insoluble content (w) of the graft copolymer obtained by centrifugation at rpm for 60 minutes was obtained, and the graft ratio was calculated by the following formula. Graft ratio (%) = 100 × {(w−1 × polyorganosiloxane component fraction in graft copolymer) / (1 × polyorganosiloxane component fraction in graft copolymer)}

[Average Particle Diameter] The average particle diameters of the polyorganosiloxane particles and the graft copolymer were measured in the latex state. As a measuring device, LEAD & NORTHRUP I
NSTRUMENTS) MICROTRAC U
Using PA, the number average particle diameter (μm) and the coefficient of variation of the particle diameter distribution (standard deviation / number average particle diameter (%)) were measured by the light scattering method.

(Production Example 1): Production of aromatic group-containing organosiloxane compound (B1) Methyltrichlorosilane (177 g), phenyltrichlorosilane (902 g) and 2500 ml of methyl isobutyl ketone as a solvent were weighed in a 5 L flask, and purified water was added. (1040 g) was gradually added over 4 hours while adjusting the internal temperature to the range of 0 to 10 ° C. After the addition was completed, trimethylchlorosilane (321 g) was added dropwise, and then at 60 ° C for 3 hours.
Stir for hours. The obtained reaction mixture was washed with water until it became neutral, and the solvent was distilled off from the separated organic phase under reduced pressure to obtain the desired organosiloxane compound (B1). N
From the MR analysis, the composition ratio represented by the average composition formula (1) is m = 0.61, n = 0.67, and therefore m + n =
The calculated values were 1.28 and n / m = 1.1.

(Production Example 2): Production of aromatic group-containing organosiloxane compound (B2) Diphenyldimethoxysilane (1200 g), M silicate 51 (578 g) manufactured by Tama Chemical Industry Co., Ltd., and methanol (435 g) were weighed into a 5 L flask. , 0.1N-H
Cl (338g) was added dropwise. After the reaction mixture was homogenized, methanol was distilled off at 100 to 120 ° C. for 6 hours. After that, toluene (2 L) was added, trimethylchlorosilane (533 g) was added, and the mixture was stirred at 60 ° C. for 3 hours. The obtained reaction mixture was washed with water until it became neutral, and the solvent was distilled off from the separated organic phase under reduced pressure to obtain the desired organosiloxane compound (B2). From the NMR analysis, the composition ratio represented by the average composition formula (1) is m = 0.
71, n = 0.76, therefore m + n = 1.4
7, n / m = 1.1 could be calculated.

(Reference Production Example 1): Production of Aromatic Group-Containing Organosiloxane Compound (B3) Methyltrichlorosilane (637 g), phenyltrichlorosilane (250 g), and 2500 ml of methyl isobutyl ketone as a solvent were weighed into a 5 L flask and purified. Water (1040 g) was gradually added over 4 hours while adjusting the internal temperature to the range of 0 to 10 ° C. After the addition was completed, trimethylchlorosilane (321 g) was added dropwise, and then at 60 ° C for 3 hours.
Stir for hours. The obtained reaction mixture was washed with water until it became neutral, and the solvent was distilled off from the separated organic phase under reduced pressure to obtain the desired organosiloxane compound (B3). N
From the MR analysis, the composition ratio represented by the average composition formula (1) is m = 1.10, n = 0.19, and therefore m + n =
The calculated values were 1.29 and n / m = 0.17.

(Production Example 3): Production of polyorganosiloxane graft copolymer (C1) An aqueous solution containing the following components was added to 1000 with a homomixer.
An emulsion was prepared by stirring at 0 rpm for 5 minutes. Ingredients Amount (parts) Pure water 251 Sodium dodecylbenzene sulfonate (SDBS) 0.5 Octamethylcyclotetrasiloxane (D4) 100 γ-Acryloyloxypropyldimethoxymethylsilane (DSA) 5

This emulsion was mixed with a stirrer, a reflux condenser,
A 5-neck flask equipped with a nitrogen blowing port, a monomer addition port, and a thermometer was collectively charged. While stirring the system, 1 part (solid content) of a 10% dodecylbenzenesulfonic acid (DBSA) aqueous solution was added, and the temperature was raised to 80 ° C over about 40 minutes, and then 80 ° C.
And reacted for 6 hours. Then, cool to 25 ℃, 20
After leaving for a while, the pH of the system was returned to 6.8 with sodium hydroxide to terminate the polymerization, and a latex containing polyorganosiloxane particles was obtained. Polymerization conversion rate is 87%, average particle size of latex of polyorganosiloxane particles is 0.15%
And the amount of toluene insoluble matter was 0%. Next, 300 parts of pure water and sodium formaldehyde sulfoxylate (SFS) 0.2 were placed in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port and a thermometer.
Parts, ethylenediaminetetraacetic acid disodium salt (EDTA)
0.01 part, 0.0025 part of ferrous sulfate and 65 parts of the polyorganosiloxane particles were charged, and the system was heated to 60 ° C. under a nitrogen stream while stirring. After reaching 60 ° C., a mixture containing 35 parts of MMA and 0.11 part of cumene hydroperoxide as a radical polymerization initiator was added dropwise over 4 hours, and then stirring was continued at 60 ° C. for 1 hour to prepare a graft copolymer. A latex was obtained.

Subsequently, the latex was diluted with pure water to a solid content concentration of 15%, and then 2 parts (solid content) of a 10% calcium chloride aqueous solution was added to obtain a coagulated slurry.
The solidified slurry was heated to 80 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane-containing graft copolymer (C1) powder. Polymerization conversion rate 9
8%, average particle diameter, and graft ratio were 42%. The solubility parameter of PMMA is 9.25 (cal
/ Cm ³ ) ^1/2 .

Other raw materials used were as follows. Polycarbonate resin: viscosity average molecular weight of about 22,000
Bisphenol A type polycarbonate resin (PC
1), a bisphenol A type polycarbonate resin (PC2) having a viscosity average molecular weight of about 19000, and a bisphenol A type polycarbonate resin (PC3) having a viscosity average molecular weight of about 17,000 Polyethylene terephthalate resin: logarithmic viscosity of 0.70
Polyethylene terephthalate resin Organic alkali metal salt: potassium perfluorobutanesulfonate (M1) Teflon (registered trademark) resin: tetrafluoroethylene (Polyflon FA-500 manufactured by Daikin Industries, Ltd.) (PTF
E)

(Example 1)Preparation of resin composition Polycarbonate resin (PC1) 100 parts by weight, production example
2 parts by weight of the silicone compound (B1) produced in 1.
Polyorganosiloxane graft copolymer prepared in Example 3
1 part by weight of body (C1) and phosphorus-based and phenol-based
ADEKA STAB HP-10 and AO-
60 (all are Asahi Denka brand names) 0.1 parts by weight each, P
After pre-dry blending 0.2 parts by weight of TFE,
Vented twin screw extrusion with the linder temperature set to 270 ° C
Machine [TEX44 (trade name): made by Japan Steel Works] hopper
And was melt-extruded to obtain a resin composition.

[0127]Liquidity evaluation Cylinder temperature 280 ℃, mold temperature 50 ℃, injection pressure 1
050 kg / cm^TwoEvaluation was made with a thickness of 3 mm.Preparation of test piece After drying the obtained pellets at 120 ° C. for 5 hours,
Using a 35t injection molding machine, cylinder temperature 310 ° C, gold
1.6 mm thickness and 3.2 mm bar (width at mold temperature 50 ° C)
12mm, length 127mm) and make the following evaluation
It was. The results are shown in Table 1.

[0128]Flame retardance evaluation According to UL-94 standard, V test with flame retardancy of 1.6mm bar
It was evaluated in the test.Impact resistance evaluation According to ASTM D-256, 2 with 3.2mm thickness bar
It was evaluated by a 3 ° C. notched Izod impact test.

(Examples 2 to 22 and Comparative Examples 1 to 17) Resins, silicone compounds, polyorganosiloxane graft copolymers, organic alkali metal salts were changed in the same manner as in Example 1 by changing the kinds and addition amounts. A composition was obtained. The pellets thus obtained were evaluated in the same manner as above. The evaluation results are shown in Tables 1 to 5.

[0130]

[Table 1]

[0131]

[Table 2]

[0132]

[Table 3]

[0133]

[Table 4]

[0134]

[Table 5]

As shown in Tables 1 to 3, the resin compositions of the respective examples satisfy all of good fluidity, high flame retardancy and excellent impact resistance. On the other hand, as shown in Tables 4 to 5, the resin composition of each comparative example does not reach a sufficient level in any of the properties.

[0136]

EFFECTS OF THE INVENTION The flame-retardant resin composition of the present invention, having the above-mentioned constitution, provides a molded article having both high flame retardancy and good fluidity and excellent impact resistance. You can Such a flame-retardant resin composition is industrially very useful.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 83:04 C08L 51:08 51:08) (72) Inventor Nobuo Miyatake Miyamae Town, Takasago Town, Takasago City, Hyogo Prefecture 1-8 F-Term inside Takasago Industrial Co., Ltd. (reference) 4J002 BN173 CG011 CG021 CP032 CP173 EV256 EV286 4J026 AB44 BA04 BA05 BA25 BA27 BA30 BA31 BA34 DB04 DB08 DB14 DB15 DB16 DB26 FA04 GA01

Claims (4)

[Claims] 1. Polycarbonate resin (A) 100 parts by weight, average compositional formula (1) R ¹ _m R ² _n SiO _{(4-m−n) / 2} (1) (wherein R ¹ has a carbon number. 1 to 4 monovalent aliphatic hydrocarbon groups, R ² represents a monovalent aromatic hydrocarbon group having 6 to 24 carbon atoms, and R ¹ and R ² each exist in two or more types. M and n are numbers satisfying 1.1 ≦ m + n ≦ 1.7 and 0.4 ≦ n / m ≦ 2.5.) Silicone compound (B) 0.1 To 20 parts by weight, and a polyorganosiloxane-containing graft copolymer (C) obtained by graft-polymerizing a vinyl-based monomer (c-2) in the presence of polyorganosiloxane particles (c-1).
A flame-retardant resin composition containing 0.1 to 20 parts by weight. 2. The silicone compound (B) represented by the average composition formula (1) has an R ³ SiO _3/2 unit (wherein R ³ is an alkyl group having 1 to 4 carbon atoms and 6 to 24 carbon atoms). Selected from the group consisting of aromatic groups, which may be the same or different) and the total of SiO ₂ units is _{2 in} all Si atoms.
The flame-retardant resin composition according to claim 1, which accounts for 0 mol% or more. 3. The polyorganosiloxane-containing graft copolymer (C) comprises a vinyl-based monomer in the presence of 40 to 90% by weight of polyorganosiloxane particles (c-1) having an average particle diameter of 0.008 to 0.6 μm. It is obtained by graft polymerization of 60 to 10% by weight of the monomer (c-2) so that the total amount becomes 100% by weight, and the vinyl monomer (c-
The flame-retardant resin composition according to claim 1 or 2, wherein 2) has a solubility parameter of the polymer of the vinyl monomer of 9.15 to 10.15 (cal / cm ³ ) ^1/2. object. 4. The flame-retardant resin composition according to claim 1, further comprising 0.01 to 5 parts by weight of an organic alkali metal salt and / or an organic alkaline earth metal salt (D). .