JP2003012910A - Polycarbonate-based flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate-based flame-retardant resin composition excellent in balance between its flame-retardancy, impact resistance, and processability, by using a flame-retardant material which is neither halogen- based nor phosphorus-based. SOLUTION: The composition comprises 100 pts.wt. of (A) a polycarbonate- based resin, 1-4.5 pts.wt. of (B) a graft copolymer containing polyorganosiloxane, 0.05-1 pts.wt. of (C) a fluorocarbon resin, and 0-2 pts.wt. of (D) an oxidation inhibitor. Adjustment is made so that silicon will account for 0.3-1.5 wt.% in the entire resin composition.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Polycarbonate resins are widely used as electric / electronic parts, OA equipment, household products or building materials because of their excellent impact resistance, heat resistance and electrical characteristics. Polycarbonate-based resins have higher flame retardancy than polystyrene-based resins, but for fields requiring high flame-retardant properties, such as electrical and electronic parts and office automation equipment, The flame retardancy is insufficient, and the addition of various flame retardants has been attempted to improve it. For example, organic halogen compounds and organic phosphorus compounds have been widely added in the past. However, many of the organic halogen-based compounds and organic phosphorus-based compounds have a problem in terms of toxicity, and in particular, the organic halogen-based compound has a problem that a corrosive gas is generated during combustion. For these reasons, in recent years, there has been an increasing demand for flame retardancy using non-halogen / non-phosphorus flame retardants.

As the non-halogen / non-phosphorus flame retardant, a polyorganosiloxane compound (also called silicone) is used.
The use of is proposed. For example, JP-A-54-36
Japanese Patent No. 365 describes that a flame-retardant resin can be obtained by kneading a silicone resin made of monoorganopolysiloxane with a polycarbonate resin.

Recently, polyorganosiloxane-containing graft copolymers have been attracting attention as having a higher flame retardancy-imparting effect than the silicone resins and the like. For example, in JP-A-2000-17029, a composite rubber-based flame retardant obtained by graft-polymerizing a vinyl-based monomer into a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber is blended with a polycarbonate-based resin. It is described that a polycarbonate-based flame-retardant resin composition can be obtained by doing so.

Japanese Unexamined Patent Publication No. 2000-226420 discloses that
A polycarbonate-based flame-retardant resin composition is obtained by blending a polycarbonate-based resin with a polyorganosiloxane-based flame retardant obtained by grafting a vinyl-based monomer onto composite particles of a polyorganosiloxane having an aromatic group and a vinyl-based polymer. It is described that it can be obtained.

Japanese Patent Laid-Open No. 2000-264935 discloses that
It is described that a polycarbonate-based flame-retardant resin composition can be obtained by incorporating a polyorganosiloxane-containing graft copolymer obtained by graft-polymerizing a vinyl-based monomer into polyorganosiloxane particles of 0.2 μm or less into a polycarbonate-based resin. Has been done.

[0007]

However, in the polycarbonate flame-retardant resin composition described in the above publication, high flame retardancy is required unless 5 parts by weight or more of the polyorganosiloxane-containing graft copolymer is added to 100 parts by weight of the polycarbonate resin. I can not get sex. For this reason, the use of a large amount of the polyorganosiloxane-containing graft copolymer raises the cost of the flame-retardant composition and deteriorates moldability and the like.

[0008]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a resin composition comprising a polycarbonate resin, a polyorganosiloxane-containing graft copolymer, a fluororesin and an antioxidant. In the above, if the silicon content in the resin composition is adjusted to a specific amount, the polyorganosiloxane-containing graft copolymer exhibits a high flame retardance with a smaller amount than before, and the cost and molding processability are improved. It was found that a polycarbonate-based flame-retardant resin composition, which is advantageous to, can be obtained, and the present invention has been completed.

That is, according to the present invention, 100 parts by weight of (A) polycarbonate resin and (B) polyorganosiloxane particles (b-1) are present in the presence of vinyl monomer (b-2).
1 to 4.5 parts by weight of a polyorganosiloxane-containing graft copolymer obtained by polymerizing the above, (C) fluororesin
A resin composition comprising 0 to 1 part by weight and (D) 0 to 2 parts by weight of an antioxidant, wherein the silicon content is 0.3 to 1.5% by weight based on 100% by weight of the total amount of the resin composition. A polycarbonate-based flame-retardant resin composition (claim 1),
The average particle diameter of the polyorganosiloxane particles (b-1) is 0.008 to 0.6 μm, and the coefficient of variation of the polycarbonate-based flame-retardant resin composition (claim 2) and the polyorganosiloxane particles is The polycarbonate-based flame-retardant resin composition according to claim 1 or 2 (claim 3) and the polyorganosiloxane-containing graft copolymer in an amount of 10 to 70% are polyorganosiloxane particles (b-1) 40.
~ 90% by weight of vinyl monomer (b-2) 60
The polycarbonate flame-retardant resin composition according to claim 1 or 2, which is a graft copolymer obtained by polymerizing 10 to 10% by weight (total 100% by weight), and polyorganosiloxane particles (b-). The polycarbonate-based flame-retardant resin composition according to claim 1, 2 or 4, wherein 1) is in the form of latex (claim 5), and the vinyl-based monomer (b-2) is a polymer of the vinyl-based monomer. Solubility parameter 9.15 ~
The polycarbonate-based flame-retardant resin composition according to claim 1 (claim 6) and the vinyl-based monomer (b-2) are 10.15 (cal / cm ³ ) ^1/2. At least one kind of monomer selected from the group consisting of a vinyl cyanide-based monomer, a (meth) acrylic acid ester-based monomer, and a carboxyl group-containing vinyl-based monomer. The polycarbonate-based flame-retardant resin composition according to claim 4 or 5 (claim 7).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate-based flame-retardant resin composition of the present invention comprises (A) polycarbonate-based resin 100.
Parts (parts by weight, the same applies hereinafter), (B) vinyl monomer (b-2) in the presence of polyorganosiloxane particles (b-1)
1 to 4.5 parts of a polyorganosiloxane-containing graft copolymer obtained by polymerizing
To 1 part and (D) 0 to 2 parts of an antioxidant, and a silicon content of 0.3 to 1 with respect to 100% (% by weight, hereinafter the same) of the total amount of the resin composition. .5
% Is what.

Polycarbonate resin (A) of the present invention
Is a preferable concrete example of the polycarbonate-based resin (A) containing a mixed resin composition containing 50% or more, and further 70% or more of polycarbonate, and is economical and has good flame retardancy-impact resistance balance. From the above, polycarbonate / polyester mixed resins such as polycarbonate, polycarbonate / polyethylene terephthalate mixed resin and polycarbonate / polybutylene terephthalate mixed resin, polycarbonate / acrylonitrile-styrene copolymer mixed resin, polycarbonate / butadiene rubber-styrene copolymer (HIPS Resin) mixed resin, polycarbonate / acrylonitrile-butadiene rubber-styrene copolymer (ABS resin) mixed resin, polycarbonate / acrylonitrile-butadiene rubber-α
-Methylstyrene copolymer mixed resin, polycarbonate / styrene-butadiene rubber-acrylonitrile-N-
A phenylmaleimide copolymer mixed resin, a polycarbonate / acrylonitrile-acrylic rubber-styrene copolymer (AAS resin) mixed resin, or the like can be used.
Further, the mixed resins may be further mixed and used.
Further, the viscosity average molecular weight of the polycarbonate used for the polycarbonate resin and the mixed resin containing the polycarbonate is 10,000 to 50,000, and further 150
Those having an amount of 00 to 25,000 are preferable from the viewpoint of moldability.

The polyorganosiloxane-containing graft copolymer (B) is a component used as a flame retardant, and the vinyl-based monomer (b-2) is polymerized in the presence of the polyorganosiloxane particles (b-1). Obtained.

The polyorganosiloxane particles (b-1) used in the polyorganosiloxane-containing graft copolymer (B) 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 particles having an average particle size of less than 0.008 μm, and if it exceeds 0.6 μm, the flame retardancy tends to deteriorate. Coefficient of variation of particle size distribution of the polyorganosiloxane particles (100 x standard deviation / average particle size)
(%) Is preferably 10 to 70 from the viewpoint that the molded product surface appearance of the resin composition containing the flame retardant of the present invention is good.
%, More preferably 20 to 60%, and particularly preferably 20 to 50%.

The polyorganosiloxane particles (b-1) in the present invention are not only particles consisting of polyorganosiloxane but also modified polyorganosiloxane containing 5% or less of other (co) polymer. It may be.
That is, the polyorganosiloxane particles are
For example, polybutyl acrylate, butyl acrylate-
You may contain 5% or less of styrene copolymers.

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

The above-mentioned organosiloxane and / or
The bifunctional silane compound is a component that constitutes the main skeleton of the polyorganosiloxane chain, and specific examples of the organosiloxane include hexamethylcyclotrisiloxane (D3) and octamethylcyclotetrasiloxane (D).
4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), etc. Is diethoxydimethylsilane, dimethoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, trifluoropropylmethyl Examples thereof include dimethoxysilane and octadecylmethyldimethoxysilane. Among these, 70 to 100%, and further 80 to 100% of D4 or the mixture of D3 to D7 or the mixture of D3 to D8 is contained from the viewpoint of good economical efficiency and flame retardancy, and diphenyl is used as the remaining component. Those containing 0 to 30%, more preferably 0 to 20% of dimethoxysilane, diphenyldiethoxysilane and the like 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 (b) described below. -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, and therefore grafting is possible.

Specific examples of the vinyl-based polymerizable group-containing silane compound include, for example, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane and γ-methacryloyl. Oxypropyldiethoxymethylsilane, γ-acryloyloxypropyldimethoxymethylsilane, γ-
(Meth) acryloyloxy group-containing silane compound such as acryloyloxypropyltrimethoxysilane, p-
Vinylphenyl group-containing silane compounds such as vinylphenyldimethoxymethylsilane and p-vinylphenyltrimethoxysilane, vinyl group-containing silane compounds such as vinylmethyldimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane, mercaptopropyltrimethoxysilane, Examples thereof include mercapto group-containing silane compounds such as mercaptopropyldimethoxymethylsilane. Among these, a (meth) acryloyloxy group-containing silane compound, a vinyl group-containing silane compound, and a mercapto group-containing silane compound are preferably used from the economical point of view.

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 type 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.

If the use ratio of the organosiloxane and the 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 them 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, The resin composition obtained by blending tends to be brittle.

The polyorganosiloxane particles (b-
1) is, for example, emulsion polymerization of a polyorganosiloxane-forming component composed of the above-mentioned organosiloxane and / or a bifunctional silane compound, a vinyl-based polymerizable group-containing silane compound, and a trifunctional or higher functional silane compound used as necessary. It is preferable to manufacture by doing.

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 by mechanical shearing in water to bring it 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 in the range of 0.02 to 0.6 μm depending on the amount of the emulsifier used. Can be controlled. The coefficient of variation of the obtained particle size distribution (100 x standard deviation / average particle size) (%) is 20 to 7
0% can be obtained.

In the case of producing polyorganosiloxane particles having a particle size distribution of 0.1 μm or less and a narrow particle size distribution, 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 emulsion-polymerized in an acidic state,
Using the obtained polyorganosiloxane particles as seeds, the remaining emulsion is additionally polymerized in the presence thereof. The polyorganosiloxane particles thus obtained are
Average particle size is 0.02-0.1 μm depending on the amount of emulsifier
And the coefficient of variation of the particle size distribution can be controlled to 10 to 60%. A more preferable method is, in place of the seed of polyorganosiloxane particles in the multi-stage polymerization,
A vinyl-based (co) polymer obtained by (co) polymerizing a vinyl-based monomer (for example, styrene, butyl acrylate, methyl methacrylate, etc.) used in the graft polymerization described below by a usual emulsion polymerization method is used. When performing multi-stage polymerization,
The average particle size of the obtained polyorganosiloxane (modified polyorganosiloxane) particles is 0.00 depending on the amount of emulsifier.
8 to 0.1 μm and the coefficient of variation of particle size distribution is 10 to 5
It can be controlled to 0%.

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 can be 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 the polymerization is preferably 60 to 120 ° C., and 70 to 10 from the viewpoint that an appropriate polymerization rate can be obtained.
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 cross-linking is more likely to be generated on the production side as the temperature becomes lower. Therefore, in order to obtain a high molecular weight or a high degree of cross-linking,
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.

Thus, when the obtained polyorganosiloxane particles are formed from, for example, an organosiloxane and / or a bifunctional silane compound or a vinyl-based polymerizable group-containing silane compound, they are usually copolymerized randomly. It becomes a polymer having a vinyl-based polymerizable group. When a trifunctional or higher functional silane compound is copolymerized, it has a crosslinked network structure. Furthermore, when a vinyl-based polymerizable group is cross-linked by a radical reaction with a radical polymerization initiator used in the below-mentioned graft polymerization, it has a cross-linked structure in which vinyl-based polymerizable groups are chemically bonded, and Part of the unreacted vinyl-based polymerizable group remains. Toluene insoluble content of the polyorganosiloxane particles (toluene insoluble content when 0.5 g of the particles is immersed in 80 ml of toluene at room temperature for 24 hours)
Is preferably 95% or less, and 90% from the viewpoint of flame retardant effect.
The following is more preferable.

By subjecting the polyorganosiloxane particles obtained in the above process to graft polymerization of the vinyl monomer (b-2), a flame retardant comprising a polyorganosiloxane-containing graft copolymer can be obtained.

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

The vinyl monomer (b-2) is a component used to obtain a flame retardant composed of a polyorganosiloxane-containing graft copolymer. Furthermore, the flame retardant is used as a thermoplastic resin. When blended to impart flame retardancy, it is also a component used to ensure compatibility between the flame retardant and the thermoplastic resin and to uniformly disperse the flame retardant in the thermoplastic resin. Therefore, as the vinyl-based monomer (b-2), the solubility parameter of the polymer of the vinyl-based monomer is 9.15 to 10.15 ((cal / cm ³ ) ^1/2 , hereinafter, the unit: (Omitted), more preferably 9.17 to 10.10, and particularly preferably 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. As the solubility parameter δc of the copolymer, the value of the main component is used when the weight fraction is less than 5%.
When the weight fraction is 5% or more, the additivity is established by the weight fraction. 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.

[0037]

[Equation 1] For example, the solubility parameter of a copolymer composed of 75% styrene and 25% acrylonitrile is substituted into the formula (1) using the solubility parameter 9.03 of polystyrene and the solubility parameter 12.71 of polyacrylonitrile, and is substituted into formula (1). The value of can be obtained.

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 obtained in each stage.

[0039]

[Equation 2] For example, polymerize in 2 stages, 75% styrene in the 1st stage
Assuming that 50 parts of a copolymer of 25% acrylonitrile and 50 parts of a polymer of methyl methacrylate are obtained in the second step, the solubility parameter of the polymer obtained in the second step is styrene. By using the solubility parameter 9.95 of the (75%)-acrylonitrile (25%) copolymer and the solubility parameter 9.25 of polymethylmethacrylate, the value of 9.60 is obtained by substituting it into the formula (2).

The amount of the vinyl-based monomer (b-2) used is 40 to 90 of the polyorganosiloxane particles (b-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 (b-2) used is too large or too small, the flame retardancy tends not to be sufficiently exhibited.

As the vinyl-based monomer (b-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, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, etc. ) Acrylic acid ester-based monomers, 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 general seed emulsion polymerization can be applied, and the polyorganosiloxane particles (b-1)
Radical polymerization of the vinyl-based monomer (b-2) may be performed in the latex. In addition, vinyl-based monomers (b-
2) may be polymerized in one step or in two or more steps.

The radical polymerization can be carried out by a method of proceeding the reaction by thermally decomposing a radical polymerization initiator, or a reaction in a redox system using a reducing agent without 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, more preferably 0.0 to 100 parts of the polyorganosiloxane particles (b-1) used.
It is preferably 1 to 10 parts, and particularly preferably 0.03 to 5 parts. When the amount of the radical polymerization initiator is less than 0.005 part, the reaction rate is low and the production efficiency tends to be poor, and when it exceeds 20 parts, heat generation during the reaction tends to be large and production tends to be difficult. is there.

Further, a chain transfer agent can be used if necessary in the 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 and n-
Examples thereof include 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 with respect to 100 parts of the vinyl-based monomer (b-2). If the amount of the chain transfer agent is less than 0.01 part, the effect used cannot be obtained, and if it exceeds 5 parts, the polymerization rate tends to be slow and the production efficiency tends to be low.

The reaction temperature during the polymerization is usually 30 to 1
It is preferably 20 ° C.

In the above-mentioned polymerization, when the polyorganosiloxane particles (b-1) contain a vinyl-based polymerizable group, when the vinyl-based monomer (b-2) is polymerized by a radical polymerization initiator, Polyorganosiloxane particles (b-
A graft is formed by reacting with the vinyl polymerizable group of 1). Polyorganosiloxane particles (b-
When a vinyl polymerizable group does not exist in 1), if a specific radical initiator such as t-butylperoxylaurate is used, hydrogen is extracted from an organic group such as a methyl group bonded to a silicon atom to generate hydrogen. The radicals cause the vinyl-based monomer (b-2) to polymerize to form a graft.

Further, 0.1 to 10%, preferably 0.5 to 5% of the vinyl-based monomer (b-2) is polymerized by using a vinyl-based polymerizable group-containing silane compound, and 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, the same as the one used in the production of the polyorganosiloxane particles (b-1) may be used. When the amount of the vinyl-based polymerizable group-containing silane compound is less than 0.1%, the vinyl-based polymerizable group-containing silane compound may be used. When the grafting ratio of the monomer (b-2) is reduced and exceeds 10%, the stability of the latex tends to be low.

In the polymerization of the vinyl-based monomer (b-2) in the presence of the polyorganosiloxane particles, the portion corresponding to the branch of the graft copolymer (here, the vinyl-based monomer (b-2) is used). Polymer) is not by-grafted onto the trunk component (here, the polyorganosiloxane particles (b-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 can be obtained as a mixture of polymers, both of them are collectively referred to as a graft copolymer in the present invention.

The flame retardant consisting of the graft copolymer obtained by emulsion polymerization may be used as it is as a latex, but since the application range is wide, it is possible to separate the polymer from the latex and use it as a powder. preferable. Examples of the method for separating the polymer include a usual method, for example, a method in which a metal salt such as calcium chloride, magnesium chloride or magnesium sulfate is added to the latex to coagulate, separate, wash, dehydrate and dry the latex. Also, a spray drying method can be used.

Thus, the polyorganosiloxane-containing graft copolymer (B) used as a flame retardant is obtained.

The fluorine-based resin (C) is a polymer resin having a fluorine atom and is a component used as a drip preventing agent during combustion. Specific examples that are preferable in that they have a large anti-dripping effect include fluorinated polyolefin resins such as polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoroethylene copolymer, and polyfluorine. Examples thereof include vinylidene chloride resin. Further, a fluorinated polyolefin resin is preferable, and a fluorinated polyolefin resin having an average particle diameter of 700 μm or less is particularly preferable. The average particle diameter here and the average particle diameter of the secondary particles formed by aggregating the primary particles of the fluorinated polyolefin resin. Further, the fluorinated polyolefin resin is preferably a fluorinated polyolefin resin having a density / bulk density ratio (density / bulk density) of 6.0 or less. The density and bulk density referred to here are JIS-K68.
It is measured by the method described in 91. The fluororesin (C) may be used alone or in combination of two or more kinds.

In the present invention, the antioxidant (D) is a component not only for suppressing oxidative decomposition of the resin during molding, but also for improving flame retardancy. . The antioxidant is not particularly limited as long as it is used in ordinary molding. Specific examples include tris [N- (3,5-di-t-butyl-4-hydroxybenzyl)] isocyanurate (Adeka Stab AO-20 manufactured by Asahi Denka Co., Ltd.), tetrakis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (manufactured by Ciba Specialty Chemicals, Irganox 1010), butylidene-1,1-bis- (2-methyl-4-hydroxy-).
5-t-butyl-phenyl) (Asahi Denka Co., Ltd., ADEKA STAB AO-40, etc.), 1,1,3-tris (2-
Methyl-4-hydroxy-5-t-butylphenyl) butane (Yoshinox 930 manufactured by Yoshitomi Fine Chemical Co., Ltd.) and other phenolic antioxidants, bis (2,6, di-t-butyl-4-methylphenyl) Pentaerythritol phosphite (Asahi Denka Co., Ltd., ADEKA STAB PEP-36, etc.), Tris (2,4-di-
t-Butylphenyl) phosphite (manufactured by Asahi Denka Co., Ltd., Adekastab 2112), 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite (manufactured by Asahi Denka Co., Ltd., Adekastab HP-10) And the like), dilauryl 3,3′-thio-dipropionate (Yoshinox DLTP manufactured by Yoshitomi Fine Chemical Co., Ltd.), dimyristyl 3,3′-
Examples thereof include sulfur-based antioxidants such as thio-dipropionate (Yoshinox DMTP manufactured by Yoshitomi Fine Chemical Co., Ltd.).

The polycarbonate flame-retardant resin composition of the present invention contains 1 to 4.5 parts, preferably 2 parts, of the polyorganosiloxane-containing graft copolymer (B) per 100 parts of the polycarbonate resin (A). ˜3 parts, 0.05 to 1 part of fluorinated resin (C), preferably 0.1 to 0.5
Parts, 0 to 2 parts of antioxidant (D), preferably 0.1 to 1
It is obtained by blending parts. However, the total amount of the composition is 1
It is necessary to adjust the composition of the polyorganosiloxane-containing graft copolymer so that the silicon content is 0.3 to 1.5%, preferably 0.7 to 1.4% with respect to 00%. If the amount of the polyorganosiloxane-containing graft copolymer (B) used is too small, the silicon content in the composition tends to be too low, and the flame retardancy tends to decrease. If it is too large, the silicon content in the composition is reduced. Not only does the amount increase too much, molding processability tends to deteriorate, but it also tends to lead to higher costs and lower market value. The silicon content can be confirmed analytically by elemental analysis. Further, if the amount of the fluororesin (C) used is too small, the flame retardancy tends to decrease, and if it is too large, the surface of the molded body tends to become rough. Further, if the amount of the antioxidant (D) used is too small, the effect of improving the flame retardancy becomes small, and if it is too large, the moldability tends to decrease.

The method for producing the polycarbonate-based flame-retardant resin composition of the present invention is not particularly limited, and a usual method can be used. For example, a method of mixing with a Henschel mixer, a ribbon blender, a roll, an extruder, a kneader and the like can be mentioned.

At this time, commonly used compounding agents, that is, plasticizers, stabilizers, lubricants, UV absorbers, pigments, glass fibers, fillers, polymer processing aids, polymer lubricants, impact modifiers, etc. Can be blended. Preferable specific examples of the polymer processing aid include methacrylate (co) polymers such as methyl methacrylate-butyl acrylate copolymer, and preferable specific examples of the impact resistance improver are butadiene rubber-based impact resistance. Examples of the property improver (MBS resin), butyl acrylate rubber-based impact modifier, butyl acrylate rubber / silicone rubber composite rubber-based impact modifier, and the like. Further, other flame retardants may be used together. For example,
Preferred specific examples of the flame retardant to be used in combination include triphenyl phosphate, condensed phosphoric acid ester, phosphorus-based compounds such as stabilized red phosphorus, cyanuric acid, triazine-based compounds such as melamine cyanurate, boron oxide, and boron such as zinc borate. Examples include system compounds. From the viewpoint of effect-cost balance, the preferable amount of these compounding agents used is 0.1 to 20 parts, more preferably 0.1 to 20 parts per 100 parts of the thermoplastic resin.
It is 2 to 10 parts, especially 0.3 to 5 parts.

The polycarbonate-based flame-retardant resin composition thus obtained may be molded by any of the molding methods used for molding ordinary thermoplastic resin compositions, that is, injection molding, extrusion molding, blow molding and calendering. A molding method or the like can be applied.

The use of the molded article obtained from the polycarbonate-based flame-retardant resin composition of the present invention is not particularly limited, but for example, desktop type computers, notebook type computers, tower type computers, server type computers, printers, copying machines. Machine, FAX
Machine, mobile phone, PHS, TV, VCR, etc.
A / Information / Household and chassis parts of home electric appliances, various building material members, various automobile members, and other applications requiring flame retardancy.

[0064]

EXAMPLES The present invention will be specifically described based on examples, but the present invention is not limited to these.

The measurements and tests in the following examples and comparative examples were carried out as follows. [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 amount] 0.5 g of solid polyorganosiloxane particles obtained by drying from latex was immersed in 80 ml of toluene at room temperature for 24 hours, and 12,000 rp
The mixture was centrifuged at m for 60 minutes, and the weight fraction (%) of the toluene-insoluble portion of the polyorganosiloxane particles was measured. [Grafting rate] 1 g of the graft copolymer was immersed in 80 ml of acetone at room temperature for 48 hours, and the rate was 6 at 12000 rpm.
The insoluble content (w) of the graft copolymer obtained by centrifugation for 0 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 diameter of the polyorganosiloxane particles and the graft copolymer is It was measured in the state of latex. As a measuring device, LEED & NORTHRUP INSTRUUM
The number average particle diameter (μm) and the variation coefficient of the particle diameter distribution (100 × standard deviation / number average particle diameter) are measured by the light scattering method using MICROTRAC UPA manufactured by ENTS).
(%) Was measured. [Silicon content] The silicon content in the polyorganosiloxane-containing graft copolymer was determined from the charged amount and the polymerization conversion rate, and the silicon content in the composition was determined from this and the blending composition ratio. [Impact resistance] The impact resistance was evaluated by an Izod test at 23 ° C. using a notched 1/8 inch bar according to ASTM D-256. [Flame Retardancy] The total combustion time of 5 samples was measured and evaluated by the vertical combustion test method based on the UL94 V test. [Moldability] Melt flow index 260 ° C,
It was measured under a load of 5 kg / cm ² and judged according to the following criteria. Good: ◯, a little bad: Δ, bad: × (Reference Example 1) Polyorganosiloxane particles (S-1)
Production of a mixture of the following components with a homomixer to 1000
An emulsion was prepared by stirring at 0 rpm for 5 minutes.

Ingredients Amount (parts) Pure water 251 Sodium dodecylbenzenesulfonate (SDBS) 0.5 Octamethylcyclotetrasiloxane (D4) 100 γ-acryloyloxypropyl dimethoxymethylsilane 5 This emulsion is stirred, reflux condenser, Nitrogen inlet,
A 5-neck flask equipped with a monomer addition port and a thermometer was charged in a batch. While stirring the system, 1 part (solid content) of a 10% aqueous solution of dodecylbenzenesulfonic acid (DBSA) was added, and the temperature was raised to 80 ° C over about 40 minutes, and then the reaction was carried out at 80 ° C for 6 hours. Then, it was cooled to 25 ° C. and left for 20 hours, then the pH of the system was returned to 6.8 with sodium hydroxide to terminate the polymerization, and a latex containing polyorganosiloxane particles (S-1) was obtained. The polymerization conversion rate, the average particle size of the latex of polyorganosiloxane particles, and the toluene insoluble content were measured, and the results are shown in Table 1.

Reference Example 2 Production of Polyorganosiloxane Particles (S-2) In a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen blowing port, a monomer addition port, and a thermometer, the component amounts ( Part) Pure water 189 SDBS 1.2 was charged. Next, the system was heated to 70 ° C. while substituting with nitrogen, and 1 part of pure water and potassium persulfate (KPS) 0.02 were added.
After adding an aqueous solution of 1 part, a mixed solution of component amount (part) styrene (St) 0.7 butyl methacrylate (BMA) 1.3 was added all at once, and the mixture was stirred for 1 hour to carry out polymerization. Upon completion, a St-BMA copolymer latex was obtained. The polymerization conversion rate was 99%. The obtained latex had a solid content of 1.0% and an average particle size of 0.01 μm. The coefficient of variation at this time was 38%.
The amount of solvent-insoluble matter in the St-BMA copolymer was 0%.

Separately, a mixture of the following components was stirred with a homomixer at 10,000 rpm for 5 minutes to prepare an emulsion of polyorganosiloxane-forming components.

Ingredients Amount (parts) Pure water 70 SDBS 0.5 D4 94 Vinyldimethoxymethylsilane 4 Next, 8 latexes containing St-BMA copolymer were added.
Keep at 0 ° C, and add 2 parts of 10% DBSA aqueous solution (solid content) to the system.
Was added, the emulsion of the polyorganosiloxane-forming component was added all at once, and the mixture was stirred for 6 hours, cooled to 25 ° C. and left for 20 hours. Then, the pH was adjusted to 6.6 with sodium hydroxide and the polymerization was terminated to obtain a latex containing polyorganosiloxane particles (S-2). The polymerization conversion rate, the average particle size of the latex of polyorganosiloxane particles, and the toluene insoluble content were measured, and the results are shown in Table 1. The polyorganosiloxane particles in the latex containing the polyorganosiloxane particles have a charged amount and a conversion ratio of the polyorganosiloxane component of 98.
% And St-BMA copolymer component 2%.

[0071]

[Table 1] (Reference Examples 3 to 7) 300 parts of pure water, sodium formaldehyde sulfoxylate (SFS) 0.2 were placed in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen blowing port, a monomer addition port and a thermometer. Parts, 0.01 parts of ethylenediaminetetraacetic acid disodium salt (EDTA), 0.002 of ferrous sulfate
5 parts and polyorganosiloxane particles shown in Table 2 were charged, and the system was heated to 60 ° C. under a nitrogen stream while stirring. After reaching 60 ° C., a mixture of the monomer and the radical polymerization initiator shown in Table 2 was added dropwise in one step or two steps over 4 hours as shown in Table 2, and then stirred at 60 ° C. for 1 hour. By continuing, a latex of the graft copolymer was obtained.

Subsequently, the latex was diluted with pure water to make the solid content concentration 15%, and then 2 parts (solid content) of a 10% calcium chloride aqueous solution was added to obtain a coagulated slurry.
Coagulation The coagulated slurry was heated to 80 ° C., cooled to 50 ° C., dehydrated, and dried to obtain powders of the polyorganosiloxane-containing graft copolymer (SG-1 to SG-5). Table 2 shows the polymerization conversion rate, average particle size, and graft rate.

In Table 2, MMA is methyl methacrylate, AN is acrylonitrile (above, monomer), CH
P is cumene hydroperoxide (radical polymerization initiator), and SP is the solubility parameter obtained by the method described in the specification.

[0074]

[Table 2] (Examples 1 to 6 and Comparative Examples 1 to 7) Polycarbonate resin flame-retardant polycarbonate resin (PC: Teflon A-2200 manufactured by Idemitsu Petrochemical Co., Ltd., viscosity average molecular weight 22000),
Polyorganosiloxane-containing graft copolymers (SG-1 to SG-5) obtained in Reference Examples 3 to 7, PTFE (polytetrafluoroethylene: polyflon FA-500 manufactured by Daikin Industries, Ltd.) and antioxidant (AO). -3
0: ADEKA STAB AO-30, HP- manufactured by Asahi Denka Co., Ltd.
10: Asahi Denka Co., Ltd. ADEKA STAB HP-10) was used and blended with the composition shown in Table 3.

The obtained blend was melt-kneaded at 280 ° C. with a twin-screw extruder (TEX44SS manufactured by Japan Steel Works, Ltd.) to produce pellets. FANUC Co., Ltd. (FAN Co., Ltd.) in which the obtained pellets were set to a cylinder temperature of 270 ° C.
A FAS100B injection molding machine manufactured by UC) was used to prepare 1/8 inch Izod test pieces and 1/16 inch flame retardancy evaluation test pieces. The obtained test pieces were used for evaluation according to the evaluation method described above.

The results are shown in Table 3.

[0077]

[Table 3] From Table 3, flame retardancy-impact resistance by blending a polycarbonate resin, a polyorganosiloxane-containing graft copolymer, a fluororesin, and an antioxidant so that the silicon content in the entire composition becomes a specific amount. It can be seen that a polycarbonate-based flame-retardant resin composition having an excellent property-molding processability balance can be obtained.

(Example 7 and Comparative Example 8) Polycarbonate / polyethylene terephthalate mixed resin flame-retardant PC, polyethylene terephthalate resin (PET: Bellpet EFG-70 manufactured by Kanebo Co., Ltd.), polyorgano obtained in Reference Example 5 Siloxane-containing graft copolymer (S
G-3), PTFE and an antioxidant (AO-30: Asahi Denka Co., Ltd. ADEKA STAB AO-30) were used in Table 4
It was compounded with the composition shown in.

The obtained blend was melt-kneaded at 260 ° C. with a twin-screw extruder (TEX44SS manufactured by Japan Steel Works, Ltd.) to produce pellets. The obtained pellets were set at a cylinder temperature of 260 ° C.
A FAS100B injection molding machine manufactured by UC) was used to prepare 1/8 inch Izod test pieces and 1/12 inch flame retardancy evaluation test pieces. The obtained test pieces were used for evaluation according to the evaluation method described above.

The results are shown in Table 4.

[0081]

[Table 4] From Table 4, flame retardancy is achieved by blending a polycarbonate / polyethylene terephthalate mixed resin, a polyorganosiloxane-containing graft copolymer, a fluororesin, and an antioxidant so that the silicon content in the entire composition is a specific amount. It can be seen that a polycarbonate-based flame-retardant resin composition having an excellent balance of properties-impact resistance-molding processability can be obtained.

[0082]

EFFECTS OF THE INVENTION According to the present invention, a polycarbonate-based flame-retardant resin composition having a good balance of flame retardancy, impact resistance, and moldability can be obtained by using a halogen-free and non-phosphorus flame retardant. be able to.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 27:12) F term (reference) 4J002 BC054 BD133 BD143 BD153 BG104 BN124 BN154 BN172 CF064 CF074 CG001 EJ016 EJ036 EJ046 EU196 EV046 EV096 EW066 FD076 FD130 FD132 FD133 GQ00 GT00 4J026 AB44 BA04 BA05 BA06 BA25 BA27 BA30 BA31 BA34 BB01 BB03 DA04 DB04 DB12 DB14 DB15 DB16 FA04 GA09

Claims (7)

[Claims] 1. A polyorganosiloxane obtained by polymerizing a vinyl monomer (b-2) in the presence of (A) 100 parts by weight of a polycarbonate resin and (B) polyorganosiloxane particles (b-1). Containing graft copolymer 1-4.
A resin composition comprising 5 parts by weight, (C) 0.05 to 1 parts by weight of a fluororesin and (D) 0 to 2 parts by weight of an antioxidant, wherein silicon is used with respect to 100% by weight of the total amount of the resin composition. A polycarbonate-based flame-retardant resin composition having a content of 0.3 to 1.5% by weight. 2. The polycarbonate-based flame-retardant resin composition according to claim 1, wherein the polyorganosiloxane particles (b-1) have an average particle size of 0.008 to 0.6 μm. 3. The polycarbonate flame-retardant resin composition according to claim 1, wherein the polyorganosiloxane particles have a coefficient of variation of 10 to 70%. 4. The polyorganosiloxane-containing graft copolymer comprises polyorganosiloxane particles (b-1) 40 to 40.
In the presence of 90% by weight, the vinyl-based monomer (b-2) 60-
The polycarbonate flame-retardant resin composition according to claim 1 or 2, which is a graft copolymer obtained by polymerizing 10% by weight (total 100% by weight). 5. Polyorganosiloxane particles (b-1)
5. The polycarbonate flame-retardant resin composition according to claim 1, which is in the form of latex. 6. The solubility parameter 9.15 to 10.1 of the vinyl monomer (b-2) is a polymer of the vinyl monomer.
The polycarbonate-based flame-retardant resin composition according to claim 1, which has a ratio of 5 (cal / cm ³ ) ^1/2 . 7. The vinyl monomer (b-2) is an aromatic vinyl monomer, a cyanide vinyl monomer, a (meth) acrylic acid ester monomer and a carboxyl group-containing vinyl monomer. The polycarbonate-based flame-retardant resin composition according to claim 1, which is at least one kind of monomer selected from the group consisting of bodies.