JPH1160931A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a non-halogen-based polycarbonate resin composition excellent in flame resistance, impact resistance and fluidity, small in differences of physical properties among molding products, hardly causing laminar peeling when carrying out a fabrication and capable of providing an improved weld adhesive strength. SOLUTION: This polycarbonate resin composition comprises (A) a polycarbonate resin and (B) a styrene resin, in combination with (C) at least one copolymer selected from following (a) to (c), and (D) a phosphoric ester not containing a halogen: (a) a copolymer composed of a formamide group-containing monomer of the formula (R1 to R6 are each H or an alkyl), and an aromatic vinylic monomer; (b) a copolymer composed of a formamide group-containing monomer of the formula, and acrylate monomer or methacrylate monomer; (c) a core-shell structural monomer comprising a core part formed out of a gummy elastomer, and a shell part covering the core part and formed out of the component (a).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition, and more particularly, to flame retardancy,
Excellent impact resistance and fluidity, with few errors in physical properties due to molded products obtained by various molding methods such as injection molding and extrusion molding, and characteristics of weld adhesion strength without delamination during molding processing The present invention relates to a polycarbonate resin composition excellent in the above.

[0002]

2. Description of the Related Art A mixture of a polycarbonate resin and a styrene resin such as an impact-resistant polystyrene resin (HIPS) or an acrylonitrile-butadiene-styrene resin (ABS resin) has excellent physical properties. It is widely used in various fields such as OA equipment, electric / electronic equipment, and automobile. Among these fields of use, there are fields where high flame retardancy is required, mainly in the field of electric and electronic devices.

Conventionally, in order to impart flame retardancy to a polymer alloy of a polycarbonate resin and a styrene resin, a halogen-based flame retardant and a flame retardant auxiliary such as antimony trioxide are often used in combination. However, in such a case, the generation of harmful substances (such as dioxins) during combustion becomes a problem, and in recent years, there has been an increasing demand for flame retardants using flame retardants (such as non-bromo) that do not contain halogen compounds.

[0004] As a method for imparting flame retardancy using the above-mentioned flame retardant containing no halogen compound, phosphorus-based flame retardants,
In particular, a method of imparting flame retardancy by using a combination of an aromatic phosphate ester flame retardant and a flame retardant auxiliary such as tetrafluoroethylene or talc has been studied.

[0005]

In recent years, molded articles have become thinner and lighter, and high impact resistance and fluidity of flame-retardant resins have also become important characteristics. As a resin composition studied and proposed for the purpose of solving all such flame retardancy, impact resistance and fluidity, it is disclosed in JP-A-8-239564 and JP-A-8-239565. Resin compositions. However, molded articles using these resin compositions have a problem in that molded articles vary during a flame retardancy test. In addition, no detailed experimental investigation has been made on these resin compositions regarding the occurrence of delamination of molded articles. Furthermore, in recent years, as the shape of a molded article has become more complicated, the weld adhesive strength after injection molding has also become important. In this regard, the above resin composition has not been studied, and sufficient reliability has not been studied. It is difficult to say that it has the fact.

The present invention has been made in view of such circumstances, and has excellent flame retardancy, impact resistance, and fluidity, and has few physical property errors due to molded products. An object of the present invention is to provide a non-halogen-based polycarbonate resin composition which does not occur and has improved weld adhesive strength.

[0007]

Means for Solving the Problems In order to achieve the above object, the polycarbonate resin composition of the present invention comprises the following components (A) to (D).

(A) Polycarbonate resin. (B) Styrene resin. (C) at least one copolymer selected from the group consisting of the following (a) to (c). (A) A copolymer comprising a monomer containing a formamide group-containing monomer represented by the following general formula (1) and an aromatic vinyl monomer as essential components. (B) a copolymer comprising a formamide group-containing monomer represented by the following general formula (1) and a monomer containing at least one of an acrylate monomer and a methacrylate monomer as an essential component; Coalescing. (C) A copolymer having a core / shell structure in which a core is formed of a rubber-like elastic material and a shell covering the core is formed in (a).

Embedded image (D) Halogen-free phosphate ester.

As described above, the inventors of the present invention have provided a mixture of a polycarbonate resin and a styrene resin with a non-halogen phosphate ester to provide a certain degree of flame retardancy and fluidity. Was obtained. And, in addition to the above flame retardancy and fluidity,
Furthermore, based on the above findings, further studies have been made for the purpose of reducing the physical property error of the resin molded product, preventing the occurrence of laminar peeling during the molding process, and improving the weld adhesive strength and impact resistance. As a result, the polycarbonate resin [component (A)] and the styrene resin [component (B)]
In order to uniformly mix and dissolve
When at least one copolymer (component (C)) selected from the group consisting of (c) is used as a compatibilizer for both resin components, it becomes possible to make both resin components compatible with each other, A polycarbonate resin composition having excellent impact resistance and processing fluidity, reduced physical property errors during molding, prevention of delamination, and improved weld strength and impact resistance can be obtained. And arrived at the present invention.

Further, by using at least one of a polytetrafluoroethylene [component (E)] and a silicone compound [component (F)] together with the above components (A) to (D), more excellent flame retardancy is obtained. Will be given.

[0011]

Next, an embodiment of the present invention will be described.

The polycarbonate resin composition of the present invention comprises:
It is obtained using the components (A) to (D).

The polycarbonate resin as the component (A) may be an aliphatic or aromatic polycarbonate resin. Examples thereof include 2,2-bis (4-hydroxyphenyl) alkane, 2-bis (4-hydroxy-3,5-dimethylphenyl) alkane,
Polymers or copolymers of bisphenols such as 2,2-bis (4-hydroxy-3,5-dipropylphenyl) alkane sulfone, sulfide and sulfoxide are exemplified. Preferably, 2,2-bis (4
-Hydroxyphenyl) propane (bisphenol A)
It is.

As the polycarbonate resin used as the component (A), a commercially available polycarbonate resin can be used in addition to the above components. Commercially available polycarbonate resins include Toughlon series (manufactured by Idemitsu Petrochemical Co., Ltd.), Iupilon series (manufactured by Mitsubishi Engineering Plastics), Panlite series (manufactured by Teijin Chemicals), Lexan series (manufactured by Nippon GE Plastics), Caliber series ( Sumitomo Dow) and the Macrolon series (Bayer).

The styrene resin as the component (B) of the present invention includes a high impact polystyrene resin (HIP) which is a composition of a styrene homopolymer or a copolymer and a rubber component.
S), ABS resin, AS resin (acrylonitrile-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethyl acrylate-styrene copolymer), and further styrene. SEBS resin (hydrogenated styrene-butadiene-styrene copolymer), SEPS resin (hydrogenated styrene-isoprene-styrene copolymer), SEP resin (hydrogenated styrene-isoprene copolymer) Hydrogenated products).

Examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polyurethane elastomer, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, and styrene-based thermoplastic elastomer. Can be

As such a styrene resin, an impact-resistant polystyrene resin is particularly preferred. A commercially available resin can be used as the impact-resistant polystyrene resin. Examples of the commercially available impact-resistant polystyrene resin include Sumibright series (manufactured by Sumitomo Chemical Co., Ltd.), Estyrene series (manufactured by Nippon Steel Chemical Co., Ltd.), and Idemitsu. Styrol HT series (manufactured by Idemitsu Petrochemical Co., Ltd.), Diaflex series (manufactured by Mitsubishi Chemical Corporation), Denka Styrol HI series (manufactured by Denki Kagaku Kogyo), Dick Styrene GH series (manufactured by Dainippon Ink and Chemicals, Inc.), Styrone series ( Asahi Kasei Kogyo Co., Ltd.), Esbrite Series (Showa Denko), Topoflex Series (Mitsui Toatsu Chemicals)
And the like.

Next, the component (C) used together with the components (A) and (B) can function as a compatibilizer. As described above, the components (a) to (c) )
At least one copolymer selected from the group consisting of

First, (a) of the component (C) will be described. The above (a) is a copolymer comprising a monomer containing a formamide group-containing monomer represented by the following general formula (1) and an aromatic vinyl monomer as essential components.

[0020]

Embedded image

In the general formula (1), preferably,
R₁, R_Two, R_Three, R_Four, R_Five, R ₆Are independent,
They are a hydrogen atom and a methyl group, respectively. Particularly preferably,
R₁, R_Two, R_Three, R_Four, R_Five, R₆Is a hydrogen atom
You.

The formamide group-containing monomer represented by the general formula (1) is described in more detail below.
N, N-diallylformamide, N, N-di- (1-methyl-2-propenyl) formamide, N, N-di-
(1-ethyl-2-propenyl) formamide, N, N
-Di- (1-n-propyl-2-propenyl) formamide, N, N-di- (1-n-butyl-2-propenyl) formamide, N, N-di- (n-hexyl-2-
Propenyl) formamide, N, N-di- (1-benzyl-2-propenyl) formamide, N, N-di- (2
-Methyl-2-propenyl) formamide, N-allyl-N- (1-methyl-2-propenyl) formamide,
N-allyl-N- (1-ethyl-2-propenyl) formamide, N-allyl-N- (2-methyl-2-propenyl) formamide and the like can be mentioned. Preferably, as previously _{described, N, R 1, R 2} , R 3, R 4, R 5, R 6 is a hydrogen atom is N- diallyl formamide.

The aromatic vinyl monomers include styrene, p-methylstyrene, α-methylstyrene, p-tert-butylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5 -Tribromostyrene and the like, which may be used alone or in combination of two or more.

Such an aromatic vinyl monomer may be used as a monomer composition in which one or more monomers copolymerizable with the aromatic vinyl monomer are used. Among such aromatic vinyl monomers, a composition containing styrene as an essential component is preferred, and styrene alone is particularly preferred.

The monomers copolymerizable with the above-mentioned aromatic vinyl monomer include acrylic acid ester monomers, methacrylic acid esters, unsaturated nitrile monomers, acrylic acid monomers and methacrylic acid monomers. , An α, β-unsaturated carboxylic anhydride and a maleimide-based monomer.

The acrylic acid ester monomer includes:
Methyl acrylate having 1 to 18 carbon atoms in the alkyl group, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, stearyl acrylate, and the like.Examples of the methacrylate monomer include:
Examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, lauryl methacrylate, and stearyl methacrylate in which the alkyl group has 1 to 18 carbon atoms. Preferable examples include ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, butyl methacrylate, octyl methacrylate, and lauryl methacrylate. And the above acrylate monomer,
The methacrylate monomer can be used as a monomer composition of one or more of an acrylate monomer and a methacrylate monomer and a copolymerizable monomer.

The unsaturated nitrile monomer includes acrylonitrile, methacrylonitrile and the like.

Examples of the α, β-unsaturated carboxylic acid anhydride include maleic anhydride and itaconic anhydride.

Among the monomers copolymerizable with these aromatic vinyl monomers, acrylic ester monomers,
Methacrylic acid ester monomers and unsaturated nitrile monomers are preferred.

In the copolymer (a) of the component (C) used in the present invention, a monomer copolymerizable with an aromatic vinyl monomer is preferably used in these monomer compositions. 0-40
% By weight, more preferably 0 to 25% by weight.

The proportion of the component derived from the formamide group-containing monomer in the copolymer (a) of the component (C) is preferably in the range of 0.05 to 20% by weight, more preferably. 0.2 to 10% by weight. Also, (C)
In the copolymer (a) as the component, the proportion of the constituent component derived from the aromatic vinyl monomer is preferably in a range of 60% by weight or more, more preferably 75% by weight or more. That is, when the proportion of the constituent part derived from the formamide group-containing monomer in the copolymer (a) of the component (C) is less than 0.05% by weight, the aromatic vinyl monomer If the proportion of the constituents derived from the body is less than 60% by weight, the obtained thermoplastic resin composition tends to have poor miscibility between the above components (A) and (B). is there. When the proportion of the constituent part derived from the formamide group-containing monomer exceeds 20% by weight, a copolymer containing the formamide group-containing monomer and the aromatic vinyl monomer as essential components [(C )) The production of component (a)] is not economical, and therefore the production of the polycarbonate resin composition is also not economical.

The proportion (addition amount) of the component derived from the formamide group-containing monomer in the copolymer (a) of the component (C) is determined based on the formyl group in the infrared absorption spectrum (IR spectrum). Can be determined. Namely, the absorbance of the absorption of the aromatic vinyl and absorption of monomer specific to derived components from body 1590～1610Cm ^-1, formamide group-containing specific to derived components from a monomer 1650～1700Cm ^-1 It can be determined using the ratio.

The weight average molecular weight of the copolymer (a) of component (C) is from 5.0 × 10 ^{3 to} 2.0 × 10 ^3
6 is preferable, and more preferably 1.0 × 10 ^{4 to} 1.0
× 10 ⁶ .

The copolymer (a) of the component (C) is an addition polymer produced by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and precipitation polymerization. Preferably, it is produced by solution polymerization or emulsion polymerization, and particularly preferably, it is produced by emulsion polymerization.

For such a copolymerization reaction of a monomer, a radical-forming catalyst such as a peroxide or an azo compound is used. The radical-forming catalyst includes benzoyl peroxide, t-butylbenzate, cyclohexane peroxide, azobisisobutyronitrile and the like, and mixtures thereof.

Among the above polymerization methods, a specific method for producing the copolymer (a) by solution polymerization includes, for example, dissolving a predetermined amount of a monomer and the above radical-forming catalyst in a solvent,
The radical generating catalyst is heated to a temperature at which radicals are generated. After reacting at the same temperature for a predetermined time, washing with a non-solvent such as methanol is repeated several times, and dried under reduced pressure,
There is a method for producing the copolymer (a).

The solvent used in the production by the solution polymerization is not particularly limited as long as it dissolves each monomer and a radical-forming catalyst and shows a liquid at the reaction use temperature. Aromatic solvents such as xylene, chlorobenzene, dichlorobenzene, and trichlorobenzene; ethyl acetate, dioxane, N, N
-Aliphatic solvents such as dimethylformamide and dimethylsulfoxide can be used.

Among the above polymerization methods, as a specific method for producing the copolymer (a) by emulsion polymerization, for example, a predetermined amount of a monomer, distilled water and a dispersion stabilizer are stirred, Disperse in water. Further, a predetermined amount of a radical generation catalyst is added, and the mixture is heated to a temperature at which radicals are generated. After a predetermined amount of reaction at the same temperature, the reaction solution is poured into a non-solvent such as methanol to precipitate a copolymer. After washing the copolymer several times with water and a non-solvent, by drying under reduced pressure,
A method for producing the copolymer as (a) is mentioned.

In the above emulsion polymerization, among the radical forming catalysts, water-soluble radical forming catalysts are preferable, and 2,2-azobis (N, N'-dimethyleneisobutylamidine) hydrochloride, 2,2-azobis (2- Amidino-propane) hydrochloride, 2- (carbamoylazo) -isobutyronitrile hydrochloride, and peroxosulfate. The amount of such a radical-forming catalyst to be added is the same as in known radical polymerization, and a particularly useful addition amount is from 0.05 to 5.0% by weight based on the monomer composition. Further, the reaction temperature needs to be sufficiently high for the radical generation catalyst to generate radicals.

As the dispersion stabilizer used in the above-mentioned production by emulsion polymerization, general surfactants are used, and particularly preferred are anionic and nonionic surfactants.

Examples of the anionic activator include fatty acid soap, rosin soap, alkylbenzene sulfonate, alkyl sulfate, alkane sulfonate, alkyl ether sulfonate, dialkyl sulfosuccinic acid, and naphthalene sulfonate formalin condensate. Examples of the nonionic activator include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, and polyvinyl alcohol. The dispersion stabilizer is used alone or in combination of two or more of these surfactants.

The reaction medium in the above-mentioned production by emulsion polymerization may be water alone or a mixture of water and one or more organic solvents. As the organic solvent,
A solvent that dissolves an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer and separates them completely without mixing when mixed with water at a volume ratio of 1: 1. If there is, it is not particularly limited. Specific examples of such an organic solvent include benzene, toluene, ethylbenzene, xylene, monochlorobenzene, dichlorobenzene, chloroform, cumene, cyclohexane, hexane, heptane, and butyl alcohol.

Next, (b) of the component (C) will be described. The above (b) can function as a compatibilizer similarly to the above (a), and comprises a formamide group-containing monomer represented by the general formula (1) and an acrylate monomer And a copolymer comprising at least one of methacrylate monomers as an essential component, which is produced by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and precipitation polymerization. Is an addition polymer. Preferably, it is produced by solution polymerization or emulsion polymerization, and particularly preferably, it is produced by emulsion polymerization. The polymerization method of the above (b) comprises the above (a)
It is the same as the above method.

The formamide group-containing monomer represented by the general formula (1) is the same as that used in the component (C) (a).

The acrylic acid ester monomer includes:
Examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, stearyl acrylate and the like in which the alkyl group has 1 to 18 carbon atoms. Further, as the methacrylate monomer, methyl methacrylate having an alkyl group having 1 to 18 carbon atoms, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate,
Lauryl methacrylate, stearyl methacrylate and the like can be mentioned. Preferred are ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, butyl methacrylate, octyl methacrylate, and lauryl methacrylate.

At least one of the above-mentioned acrylate monomer and methacrylate monomer can be used as a monomer composition using one or more monomers copolymerizable with these ester copolymers. It is. The monomers copolymerizable with the ester copolymer include aromatic vinyl monomers, unsaturated nitrile monomers, acrylic acid monomers, methacrylic acid monomers, α, β-unsaturated carboxylic acids. Acid anhydrides and maleimide monomers are exemplified. As these monomers, those similar to those described in the above (a) can be mentioned. The monomer copolymerizable with at least one of the acrylic acid ester monomer and the methacrylic acid ester monomer is preferably used in the monomer composition in an amount of 0 to 50% by weight, more preferably 0 to 50% by weight. It is used in the range of ３０30% by weight.

The proportion of the component derived from at least one of the acrylate monomer and the methacrylate monomer in the copolymer (b) is preferably 50% by weight or more. , More preferably 7
0% by weight or more. Further, the proportion of the component derived from the formamide group-containing monomer in the copolymer as the component (b) is preferably 0.05 to 20% by weight, more preferably 0.2 to 10% by weight. It is. That is, in the copolymer (b), when the proportion of the component derived from the formamide group-containing monomer is less than 0.05% by weight, or when the acrylate monomer and the methacrylate ester are used alone. When at least one of the monomers is less than 50% by weight in the monomer composition, the resulting polycarbonate resin composition has an insufficient effect of improving the impact resistance and an effect of improving the weld adhesive strength. This is because it becomes insufficient.

The proportion (addition amount) of the component derived from the formamide group-containing monomer in the copolymer (b) of the component (C) is determined by the formyl group in the infrared absorption spectrum (IR spectrum). Can be determined. That is, the absorption around 1720 cm ^-1 specific to the component derived from at least one of the acrylate monomer and the methacrylate monomer, and the absorption specific to the component derived from the formamide group-containing monomer.
It can be determined using the absorbance ratio of the absorption around 650 to 1700 cm ^-1 .

The weight average molecular weight of the copolymer (b) of the component (C) is preferably from 5.0 × 10 ^{3 to} 2.0.
× 10 ⁶ , more preferably 1.0 × 10 ⁴ to 1.
It is 0 × 10 ⁶ .

In the components (a) and (b) of the component (C), for example, the component (a) is represented by the general formula (1)
A copolymer comprising at least one of an acrylate ester monomer and a methacrylate ester monomer together with a formamide group-containing monomer represented by ) Is obtained by using an aromatic vinyl monomer together with the formamide group-containing monomer represented by the general formula (1) and at least one of an acrylate monomer and a methacrylate monomer. In the case of a copolymer, both have the same monomer component. However, the above (a) contains a formamide group-containing monomer and an aromatic vinyl monomer as essential components, and the above (b) shows a formamide group-containing monomer, an acrylic acid ester monomer and a methacrylic acid ester monomer. Since at least one of the monomers has an essential component, the ratio of the aromatic vinyl-based monomer is higher (a), excluding the formamide group-containing monomer, which is a common essential component, and acrylic acid The case where the proportion of at least one of the ester monomer and the methacrylate monomer is larger is (b).

Next, (c) of the component (C) will be described. The above (c) can function as a compatibilizer similarly to the above (a) and (b), and the core portion is formed of a rubber-like elastic body, and the shell portion covering the core portion is It is a copolymer having a core / shell structure formed of the copolymer (a).

The rubber-like elastic body forming the core (core component) is derived from at least one of an acrylate monomer and a methacrylate monomer, or a substance mainly composed of an organosiloxane. It is composed of

The acrylic acid ester monomer includes:
Examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, stearyl acrylate and the like in which the alkyl group has 1 to 18 carbon atoms. Further, as the methacrylate monomer, methyl methacrylate having an alkyl group having 1 to 18 carbon atoms, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate,
Lauryl methacrylate, stearyl methacrylate and the like can be mentioned. Preferred are ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, butyl methacrylate, octyl methacrylate, and lauryl methacrylate.

In the case where the rubber-like elastic body is composed of one derived mainly from at least one of an acrylate monomer and a methacrylate monomer, the general formula (1) Can be copolymerized in the range of 0 to 20% by weight.

Similarly, when the rubber-like elastic material is composed of one derived mainly from at least one of an acrylate monomer and a methacrylate ester, the rubber-like elastic material may be crosslinked. The crosslinking agent may be used in the range of 0 to 2% by weight. Examples of the crosslinking agent include an alkylene glycol diacrylate having an alkyl group having 2 to 4 carbon atoms and an alkylene glycol dimethacrylate having an alkyl group having 2 to 4 carbon atoms. Is raised. Examples include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate.

In the case where the rubber-like elastic body is composed of one derived mainly from at least one of an acrylate monomer and a methacrylate ester monomer, It can also be used as a monomer composition in which one or more monomers copolymerizable with the above are used in combination.

The above copolymerizable monomers include aromatic vinyl monomers, unsaturated nitrile monomers, acrylic acid monomers, methacrylic acid monomers, α, β-unsaturated carboxylic anhydrides. And maleimide-based monomers. The monomer copolymerizable with at least one of the acrylic acid ester monomer and the methacrylic acid ester monomer is preferably used in the monomer composition in an amount of 0 to 50% by weight, more preferably 0 to 50% by weight. It is used in the range of ３０30% by weight.

The rubber-like elastic body composed of one derived from at least one of the above-mentioned acrylate monomer and methacrylate monomer is
It is preferably produced by emulsion polymerization, and the emulsion polymerization is carried out in the same manner as the emulsion polymerization described in the above (a) and (b).

In a rubber-like elastic body derived from one mainly composed of at least one of the above-mentioned acrylate monomer and methacrylate ester monomer, the acrylate monomer and the methacrylate ester The proportion of the component derived from a monomer mainly composed of at least one of the monomers is preferably in the range of 50 to 100% by weight, and more preferably 70 to 100% by weight. Further, the proportion of the component derived from the formamide group-containing monomer is preferably in the range of 0 to 20% by weight, more preferably 0.2 to 10% by weight. Further, the proportion of the component derived from the crosslinking component is preferably in the range of 0 to 2% by weight, more preferably 0.01 to 0.1% by weight.
It is. That is, in the core portion (c) of the above (c), the ratio of the component derived from a monomer mainly composed of at least one of an acrylate monomer and a methacrylate monomer is 50% by weight. When the content is less than 2%, or when the proportion of the component derived from the crosslinking component exceeds 2% by weight, the effect of improving the impact resistance of the obtained polycarbonate resin composition is insufficient, and the weld strength of the weld resin is insufficient. This is because the improvement effect becomes insufficient.

On the other hand, examples of the organosiloxane monomer include dimethylsiloxane and various cyclic members having three or more members, and preferably a three- to six-membered ring. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like.

When the rubber-like elastic material is composed of a monomer derived from the above-mentioned organosiloxane-based monomer, a crosslinking agent and a graft-crosslinking agent are used in addition to the organopolysiloxane monomer. Can be used together.

As the crosslinking agent used for the rubber-like elastic material derived from the above-mentioned monomer mainly composed of an organosiloxane, a trifunctional or tetrafunctional silane crosslinking agent such as trimethoxymethylsilane or trimethoxymethylsilane Examples include ethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane and the like. Preferred are tetrafunctional silane crosslinking agents, and particularly preferred is tetraethoxysilane. The crosslinking agent can be used in a monomer mainly composed of organosiloxane in a range of 0.1 to 30% by weight.

The graft-crosslinking agent used for the rubber-like elastic material derived from the above-mentioned monomer mainly composed of an organosiloxane is used for graft polymerization of an acrylate monomer and a methacrylic acid ester monomer described below. It is what you need. This grafting agent can be used in a range of 0.1 to 10% by weight in a monomer mainly composed of an organosiloxane.

Examples of the graft crosslinking agent include acryloyloxysiloxane, methacryloyloxysiloxane, vinylsiloxane and the like. Of the acryloyloxysiloxane and methacryloyloxysiloxane, methacryloyloxysiloxane is preferred. Examples of the methacryloyloxysiloxane include, for example, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl Ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane and the like. Examples of the vinyl siloxane include tetramethyltetravinylcyclotetrasiloxane. Further, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane and the like can also be used as a graft crossing agent. These grafting agents can be used in a range of 0 to 10% by weight in the monomer mainly composed of organosiloxane.

As a method for producing the rubber-like elastic material derived from the above-mentioned monomer mainly composed of an organosiloxane, a production method by emulsification and aggregation is preferable. For example, a mixed solution of an organosiloxane, a crosslinking agent and a graft cross-linking agent is used. And an emulsion polymerization method in which polymerization is carried out in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid and alkylsulfone. The use of the above-mentioned alkylbenzenesulfonic acid is particularly preferable because it functions as an emulsifier for the organosiloxane and also functions as a polymerization initiator.
Further, when a metal salt of an alkyl benzene sulfonic acid or a metal salt of an alkyl sulfonic acid is used in combination, the graft polymerization of an acrylate monomer and a methacrylate monomer described below, and the core / shell structure (c), In the polymerization of the shell part, it is more preferable because it is effective to maintain the polymer stably.

The rubber-like elastic body derived from the above-mentioned organosiloxane-based monomer can be graft-polymerized with an acrylate monomer and a methacrylate monomer. Further, together with these monomers, the formamide group-containing monomer represented by the general formula (1) is added to the acrylate ester monomer and the methacrylate ester monomer in an amount of 0 to 20% by weight. Can be copolymerized.

The acrylate monomer includes:
Examples thereof include ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate in which the alkyl group has 1 to 18 carbon atoms. Examples of the methacrylate monomer include 2-ethylhexyl methacrylate and lauryl methacrylate having an alkyl group having 1 to 18 carbon atoms. Of these, particularly preferred are:
It is butyl acrylate.

In the above graft polymerization, a crosslinking agent can be used. Examples of the crosslinking agent include alkylene glycol diacrylates having 2 to 4 carbon atoms in the alkyl group.
Alkylene glycol dimethacrylate is exemplified.
Examples include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate. Allyl methacrylate also acts as a crosslinking agent. These crosslinking agents can be used in the acrylate ester monomer and the methacrylate ester monomer in the range of 0 to 20% by weight.

An acrylic acid ester monomer and a methacrylic acid ester monomer produced by the above graft polymerization;
The component derived from the formamide group-containing monomer and the crosslinking agent can be blended at a ratio of 0 to 90% by weight in the component of the rubber-like elastic body derived from the monomer mainly containing organosiloxane. is there.

As the rubber-like elastic body derived from such a monomer mainly composed of an organosiloxane, commercially available fine particles of a silicone resin can be used. For example, Toshiba Silicone Co., Ltd. Tospearl 10
5, Tospearl 120, Tospearl 130 and the like.

In the core / shell structure copolymer (c), the shell (shell) covering the core (core) is composed of the component (C) and the component (a). It is constituted by copolymerizing similar monomer components. Therefore, among the components (c) of the component (C), regarding the monomers used for the polymerization of the shell (shell portion) and the proportions of the components derived from these monomers, etc., the components (C) This is exactly the same as the above (a).

The proportion of the core (shell) and the shell (shell) in component (c) of component (C) is (c) 100% by weight (total of the core and shell). If so, the core portion is preferably in the range of 10-70% by weight, more preferably 20-50% by weight, and therefore the shell portion is preferably in the range of 30-90% by weight,
More preferably, it is 50 to 80% by weight. That is, if the core portion is less than 10% by weight, the effect of improving the weld adhesive strength of the obtained polycarbonate resin composition tends to be insufficient.

The polymerization reaction of the copolymer (c) having the core / shell structure is preferably carried out by emulsion polymerization. Specifically, according to the above-mentioned method, first, the core portion of (c) becomes An emulsion of the copolymer constituting the rubber-like elastic body is prepared. Then, a predetermined amount of a monomer (monomer similar to (a) in the component (C)) and a radical-producing catalyst are added to the emulsion, and a predetermined amount of the monomer (c) becomes a shell portion. By performing polymerization in the same manner as the method used in the above (a) and (b) of the components,
(C) a method of producing a copolymer having a core / shell structure.

The proportion (addition amount) of the component derived from the formamide group-containing monomer in the copolymer (c) of the component (C) is determined by the formyl group in the infrared absorption spectrum (IR spectrum). Can be determined. That is, the absorption at 1590 to 1610 cm ^-1 specific to the component derived from the aromatic vinyl monomer, and the specific component derived from at least one of the acrylate monomer and the methacrylate monomer. Absorption around 1720 cm ^-1 , and 1650-1 -1 which is characteristic of a component derived from a formamide group-containing monomer.
It can be determined using the absorbance ratio of the absorption near 700 cm ^-1 .

Further, in the above component (C),
The weight ratio (% by weight) of the core portion and the shell portion can be determined by an infrared absorption spectrum (IR spectrum). That is, the core portion is shown below (x
In the case of 1), the absorption around 1720 cm ⁻¹ peculiar to the component derived from at least one of an acrylate monomer and a methacrylate monomer, and the case where the core portion is as shown below (x2) Are 1020 to 1090, which are characteristic of components derived from organosiloxanes.
cm ^-1 , while the shell portion is 1590-1610c, characteristic of components derived from aromatic vinyl monomers.
It can be determined using the absorbance ratio of the absorption at m ^-1 .

(X1) The ratio of constituent components derived from those mainly composed of at least one of an acrylate monomer and a methacrylate monomer is 50 to 100.
% By weight, the proportion of the component derived from the formamide group-containing monomer represented by the general formula (1) is 0 to 20% by weight, and the proportion of the component derived from the crosslinking component is 0 to 20% by weight.
2% by weight of a rubber-like elastic body. (X2) A rubber-like elastic body in which the proportion of a component derived from a monomer mainly composed of an organosiloxane is 10 to 100% by weight.

[0077] In the above-mentioned embodiments (a) to (c) of the use of the component (C), from the viewpoint of further improving the Izod impact strength and the weld strength, the components (a) and (b) are preferably used. ) Or (c) alone.

Next, in the present invention, the above (A) to (A)
The halogen-free phosphoric acid ester, which is the component (D) used together with the component (C), has a function as a flame retardant, and is a single phosphoric acid monomer represented by the following general formula (2) or An oligomer or a mixture of two or more phosphate ester monomers or oligomers.

[0079]

Embedded image

Examples of the component (D) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxy phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, and the like. Can be
These may be used alone or in combination of two or more. Among them, triphenyl phosphate or an oligomer thereof is preferably used.

As the component (D), a commercially available halogen-free phosphoric acid ester monomer can be used in addition to the above components. For example, TP manufactured by Daihachi Chemical Co., Ltd.
P, TCT, TOP, PX-130 and the like. Also, a commercially available halogen-free phosphate ester oligomer can be used. For example, CR-7 manufactured by Daihachi Chemical Co., Ltd.
33S, CR-733RS and the like.

The polycarbonate resin composition of the present invention contains, as an optional component, polytetrafluoroethylene (P) in addition to the essential components (A) to (D).
At least one of TFE) [component (E)] and silicone compound [component (F)] can be blended.

The above polytetrafluoroethylene (PTF)
E) [Component (E)] is used as an anti-dripping agent, and preferably has an average molecular weight of 500,000 or more, particularly preferably 500,000 to 1
0,000,000. As the polytetrafluoroethylene (PTFE), all currently known polytetrafluoroethylene can be used. In particular, polytetrafluoroethylene (PTFE) having fibril-forming ability can impart higher flame retardancy.

The above polytetrafluoroethylene (PTF)
As E) [component (E)], commercially available polytetrafluoroethylene can be used. For example, Teflon 6
-J (manufactured by Du Pont-Mitsui Fluorochemicals), Polyflon D-1, Polyflon F-103, Polyflon MPA
FA-100, polyflon MPA FA-500,
Polyflon F201 (manufactured by Daikin Industries, Ltd.), Algoflon F5 (manufactured by Montefluos) and the like. These polytetrafluoroethylene (PTFE) may be used alone or in combination of two or more.

The above silicone compound [component (F)]
Like the component (E), it is used as an anti-dripping agent, and a powdered silicone resin can be used. Further, any of the currently known silicone resins can be used.

As the silicone compound [component (F)], commercially available silicone compounds can be used, and examples thereof include Si powder series (manufactured by Dow Corning).

Next, the contents of the components (A) to (D) as essential components and the components (E) and (F) as optional components in the polycarbonate resin composition of the present invention will be described.

Regarding the mutual mixing ratio of the component (A) and the component (B), the sum of the two components [(A) + (B)] is 10
Component (A) is preferably used in an amount of 50 to 90 parts by weight based on 0 parts by weight.
Parts by weight, more preferably 50 to 85 parts by weight,
Component (B) is preferably added in an amount of 50 to 10 parts by weight, more preferably 50 to 15 parts by weight. That is, the above (A)
If the mutual proportion of the component and the component (B) is outside the above range,
This is because a mechanical strength such as an impact strength of the obtained polycarbonate resin composition tends to decrease.

Next, the above component (C) [(a) to (c)
At least one copolymer selected from the group consisting of)
Is preferably 0.05 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). That is, when the component (C) is less than 0.05 part by weight, the miscibility of the component (A) and the component (B) is poor, and the mechanical strength such as the impact strength of the obtained polycarbonate resin composition is reduced, and the physical properties are reduced. May not be able to obtain the effect of improving. Further, even if it is added in an amount exceeding 20 parts by weight, no further effect corresponding to the amount added in excess of the above-mentioned amount can be recognized, which is economically disadvantageous in producing a polycarbonate resin composition. It is.

The component (D) is preferably used in an amount of 2 to 100 parts by weight in total of the components (A) and (B).
20 parts by weight, more preferably 5 to 15 parts by weight.
That is, if the component (D) is less than 2 parts by weight, it is difficult to obtain the desired flame retardancy, and if it exceeds 20 parts by weight, the mechanical strength such as impact strength of the obtained polycarbonate resin composition tends to decrease. Is seen.

When the above-mentioned component (E), which is an optional component, is contained, its content is set to 5 parts by weight or less based on 100 parts by weight of the total of the components (A) and (B). Is preferred, more preferably 0.05 to 5 parts by weight,
Particularly preferably, it is in the range of 0.08 to 0.5 part by weight.
That is, when the component (E) exceeds 5 parts by weight, it is difficult to obtain a further effect of preventing dripping of the melt, and furthermore, the mechanical strength such as the impact strength of the obtained polycarbonate resin composition is reduced, and the moldability is adversely affected. This is because the

When the above-mentioned component (F), which is an optional component, is contained, its content is set to 20 parts by weight or less based on 100 parts by weight of the total of the components (A) and (B). Is more preferable, more preferably 0.5 to 20 parts by weight, particularly preferably 1 to 15 parts by weight. That is, if the amount of the component (F) exceeds 20 parts by weight, it is difficult to obtain a further effect of preventing the molten dripping, and further, the mechanical strength such as the impact strength of the obtained polycarbonate resin composition is reduced, and the moldability is adversely affected. This is because the

The polycarbonate resin composition of the present invention comprises:
The above components (A) to (D) are used as essential components, and optional components (E) and (F) are used as components. However, if necessary, other additives, for example, may be used. ,
Glass fiber, carbon fiber and other reinforcing agents, talc,
An inorganic filler such as mica, a heat stabilizer, an antistatic agent, an antioxidant, an ultraviolet absorber and the like may be appropriately added.

The method of mixing the above components (A) to (D) and the optional components (E) and (F) in the production of the polycarbonate resin composition of the present invention includes, for example,
A melt mixing method is used. As to the method of adding each component, for example, at least a predetermined amount of the component (A), the component (B), the component (C) and the component (D), and optionally at least the component (E) and the component (F) A method in which one is preliminarily mixed in a pellet or powder and heated and melt-mixed, or (A) and (C) and (D), and optionally (E) and (F) A similar polycarbonate resin composition can be obtained by adding the component (B) to a composition in which at least one of them is melt-mixed in advance and melt-mixing.

A more specific method for producing the polycarbonate resin composition of the present invention will be described. That is, the components (A) to (D) and the optional components are obtained by using a kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, or a kneading roll, or a mixer such as a Henschel mixer (E). )
At least one of component (F) and other additives may be mixed in a heat-melted state. The heating melting temperature varies depending on the type and blending amount of each component and the physical properties of the polycarbonate resin composition, but is usually 240 ° C to 300 ° C.
It is.

In the present invention, the compatibilizing agent, which is the component (C), acts on the dispersion interface of both the resins (A) and (B) to form an interfacial tension between the dispersed phase and the matrix phase. And has the effect of stabilizing the dispersion interface.

Next, examples will be described together with comparative examples.

First, the component (C) is produced according to the following production method.

[Production Example of Copolymer a-1 to be Component (a) of Component (C)] 1000 ml equipped with a stirrer, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen inlet tube.
94 g of styrene, 6 g of N, N-diallylformamide, sodium alkylbenzenesulfonate 3
g of water and 397 g of water and stirred at high speed to disperse the monomer composition. Then, 30 g of a 3% aqueous solution of ammonium persulfate was added, and the mixture was reacted at 70 ° C. for 6 hours. Then, after cooling the reaction solution to 30 ° C., the reaction solution is stirred for 5 minutes.
It was poured into 000 ml of methanol to precipitate a copolymer. After repeating filtration and washing with methanol using this copolymer, the copolymer a-1 was obtained by drying under reduced pressure.
I got This copolymer a-1 is 1.5 wt% formyl group content than the peak intensity of 1660 cm ^-1 and 1600 cm ^-1 by IR spectroscopy, the weight average molecular weight from gel permeation chromatography measurement 5.1 × 10 ⁵ was measured.

[Production Example of Copolymer a-2 to be (a) of Component (C)] 1000 ml equipped with a stirrer, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen inlet tube.
5 g of α-methylstyrene and 85 of styrene
g, 15 g of N, N-di (2-methylpropenyl) formamide, 2 g of sodium lauryl sulfate, and 380 g of water and stirred at high speed to disperse the monomer composition.
17 g of a 3% aqueous solution of 2,2-azobis (2-amidino-propane) hydrochloride was added, and the mixture was reacted at 70 ° C. for 6 hours.
Then, after the reaction solution was cooled to 30 ° C., the reaction solution was poured into 5000 ml of methanol with stirring to precipitate a copolymer. After repeating filtration and washing with methanol using the copolymer, drying was performed under reduced pressure to obtain a copolymer a-2. This copolymer a-2 is 1660 cm ^-1, and a formyl group content than the peak intensity of 1600 cm ^-1 is 2.0 wt% by IR spectroscopy, the weight average molecular weight from gel permeation chromatography measurement 8.0 × 10 ⁴ was measured.

[Production Example of Copolymer b-1 to be Component (b) of Component (C)] 1000 ml equipped with a stirrer, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen inlet tube.
After charging 94 g of butyl acrylate, 6 g of N, N-diallylformamide, 3 g of rosin soap, and 397 g of water into the flask, stirring at high speed to disperse the monomer composition,
Add 30 g of a 3% aqueous solution of ammonium persulfate,
For 4 hours. Then, after cooling the reaction solution to 30 ° C., the reaction solution was poured into a 5% aqueous magnesium sulfate solution to precipitate a copolymer. After repeating filtration and water washing using this copolymer, it was dried under reduced pressure to obtain a copolymer b-1. This copolymer b-1 has an IR
1660 cm ^-1 and 1720c by spectral measurement
The formyl group content is 1.6% by weight based on the peak intensity of m ^-1.
The weight average molecular weight was determined to be 8.9 × 10 ⁵ by gel permeation chromatography.

[Production Example of Copolymer b-2 to be Component (b) of Component (C)] 1000 ml equipped with a stirring device, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen introducing tube.
40 g of stearyl acrylate, 50 g of lauryl methacrylate, N, N-diallylformamide 10
g, polyoxyethylene alkyl allyl ether 1.5
g, 1.5 g of rosin soap and 380 g of water were stirred at high speed to disperse the monomer composition. Then, 30 g of a 3% aqueous solution of ammonium persulfate was added and reacted at 70 ° C. for 4 hours. Then, after cooling the reaction solution to 30 ° C.,
The reaction solution was poured into a 5% aqueous magnesium sulfate solution to precipitate a copolymer. After repeating filtration and water washing using this copolymer, drying was performed under reduced pressure to obtain a copolymer b-2. The copolymer b-2 is 1.5 wt% formyl group content than the peak intensity of 1660 cm ^-1 and 1720 cm ^-1 by IR spectroscopy, the weight average molecular weight from gel permeation chromatography measurement 8.0 × 10 ⁴ was measured.

[Production Example of Copolymer c-1 to be Component (c) of Component (C)] 1000 ml equipped with a stirrer, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen inlet tube.
80 g of butyl acrylate, 4 g of N, N-diallylformamide, 0.08 g of ethylene glycol dimethacrylate, 6 g of sodium alkylbenzenesulfonate, and 483 g of water were charged into the flask and stirred at high speed to disperse the monomer composition. Then, 17 g of a 3% aqueous solution of ammonium persulfate was added and reacted at 70 ° C. for 4 hours. Then
120 g of styrene, 6 g of N, N-diallylformamide
Was stirred at a high speed to disperse the monomer composition, and 26 g of a 3% aqueous solution of ammonium persulfate was added.
The reaction was performed at 0 ° C. for 4 hours. After cooling the reaction solution to 30 ° C., the reaction solution was poured into a 5% aqueous solution of magnesium sulfate to precipitate a copolymer. Filtration using this copolymer
After repeated washing with water, drying is performed under reduced pressure, whereby a copolymer composed of butyl acrylate, N, N-diallylformamide and ethylene glycol dimethacrylate is used as a core in styrene and N, N-diallylformamide. A copolymer c-1 having a core / shell structure in which the resulting copolymer was a shell portion was obtained. This copolymer c-1
Is 1600 cm ⁻¹ , 166 by IR spectrum measurement.
Formyl group content than the peak intensity of the 0 cm ^-1 and 1720 cm ^-1 was 1.6 wt%. Also, this core /
In the copolymer c-1 having a shell structure, the core portion was 40.2% by weight and the shell portion was 59.8% by weight.

[Copolymer of Component (C) to be (c)]
Production Example of c-2] Stirring device, heating device, dropping funnel, temperature
1000ml equipped with a thermometer, reflux cooling device and nitrogen inlet tube
40 g of lauryl methacrylate and N, N-di
Allyl formamide 2 g, propylene glycol dimeta
0.04 g of acrylate, 6 g of rosin soap, and 483 g of water
The mixture was stirred at a high speed to disperse the monomer composition.
Thereafter, 8 g of a 3% aqueous solution of ammonium persulfate was added, and 70%
The reaction was performed at 4 ° C. for 4 hours. Then, 160 g of styrene,
Charge N, N-diallylformamide 8g and stir at high speed
After dispersing the monomer composition, perform ammonium persulfate
34 g of a 3% aqueous solution of sodium chloride was added and reacted at 80 ° C. for 4 hours.
I let you. After cooling the reaction solution to 30 ° C., the reaction solution was
Put into 5% aqueous magnesium sulfate solution to precipitate copolymer
I let it. Filtration and water washing were repeated using this copolymer.
Thereafter, by drying under reduced pressure, lauric methacrylate
Ryl and N, N-diallylformamide and propylene
Copolymer consisting of glycol dimethacrylate is the core
From styrene and N, N-diallylformamide
Of core / shell structure in which the copolymer is a shell part
Merged c-2 was obtained. This copolymer c-2 has an IR spectrum.
1600cm ^-1, 1660cm^-1and
1720cm^-1Formyl group content from the peak intensity of
It was 1.6% by weight. In addition, this core / shell structure
The copolymer c-2 had a core portion of 19.9% by weight and a shell
The portion was 80.1% by weight.

[Production Example of Copolymer c-3 as Component (C) of Component (C)] 1000 ml equipped with a stirrer, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen inlet tube.
120 g of butyl acrylate, 6 g of N, N-diallylformamide, 0.12 g of ethylene glycol dimethacrylate, 6 g of sodium alkylbenzenesulfonate, and 483 g of water were charged into the flask and stirred at high speed to disperse the monomer composition. Then, 26 g of a 3% aqueous solution of ammonium persulfate was added and reacted at 70 ° C. for 4 hours. Then, 80 g of styrene, N, N-diallylformamide 4
g, stirred at high speed to disperse the monomer composition, and then added 17 g of a 3% aqueous solution of ammonium persulfate.
The reaction was performed at 80 ° C. for 4 hours. After cooling the reaction solution to 30 ° C., the reaction solution was poured into a 5% aqueous solution of magnesium sulfate to precipitate a copolymer. After repeating filtration and washing with water using this copolymer, drying was carried out under reduced pressure, whereby a copolymer comprising butyl acrylate, N, N-diallylformamide and ethylene glycol dimethacrylate was formed in the core portion of styrene. And a copolymer c-3 having a core / shell structure in which the copolymer comprising N, N-diallylformamide is a shell part. This copolymer c-3
Is 1600 cm ⁻¹ , 166 by IR spectrum measurement.
Formyl group content than the peak intensity of the 0 cm ^-1 and 1720 cm ^-1 was 1.5 wt%. Also, this core /
The copolymer c-3 having a shell structure had a core portion of 60.5% by weight and a shell portion of 39.5% by weight.

[Production Example of Copolymer c-4 to be Component (c) of Component (C)] 1000 ml equipped with a stirrer, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen inlet tube.
483 g of water, 6 g of sodium alkylbenzenesulfonate, silicone resin particles (Tospearl 10)
5, manufactured by Toshiba Silicone Co., Ltd.), and dispersed by stirring at high speed. 160 g of styrene and 8 g of N, N-diallylformamide were stirred at high speed to disperse the monomer composition. 34 g of a 3% aqueous solution of ammonium sulfate was added and reacted at 80 ° C. for 4 hours. After cooling the reaction solution to 30 ° C., the reaction solution was poured into a 5% aqueous solution of magnesium sulfate to precipitate a copolymer. After repeating filtration and water washing using this copolymer, by performing drying under reduced pressure, the silicone resin particles are formed in the core,
A copolymer c-4 having a core / shell structure in which a copolymer composed of styrene and N, N-diallylformamide was a shell portion was obtained. The copolymer c-4 by IR spectroscopy, formyl group content than the peak intensity of 1600 cm ^-1 and 1660 cm ^-1 was 1.1 wt%.
In addition, 1020~1090cm ^-1 and 1600cm ^-1
From the peak strength, the core portion was 20.2% by weight and the shell portion was 79.8% by weight.

[Production Example of Copolymer c-5 to be Component (c) of Component (C)] 1.6 g of tetraethoxysilane, 80 g of octamethylcyclotetrasiloxane, 0.8 g of sodium alkylbenzenesulfonate, alkylbenzenesulfonic acid After 0.8 g and 163 g of water were preliminarily stirred with a homomixer at 10,000 rpm, they were emulsified and dispersed with a homogenizer at a pressure of 300 kg / cm ² . This emulsion is stirred, a heating device, a dropping funnel, a thermometer,
The mixture was charged into a 1000 ml flask equipped with a reflux cooling device and a nitrogen inlet tube, stirred at high speed, and reacted at 80 ° C. for 5 hours. This reaction solution was left at 20 ° C., and after 48 hours, neutralized to pH 4.9 with an aqueous sodium hydroxide solution. Then, 120 g of styrene, 6 g of N, N-diallylformamide, 5 g of sodium alkylbenzenesulfonate, and 320 g of water were charged and stirred at a high speed to disperse the monomer composition. Then, 26 g of a 3% aqueous solution of ammonium persulfate was added.
In addition, the reaction was carried out at 80 ° C. for 4 hours. This reaction solution is kept at 30
After cooling, the reaction solution was poured into a 5% aqueous solution of magnesium sulfate to precipitate a copolymer. After repeating filtration and water washing using this copolymer, by drying under reduced pressure, a copolymer composed of tetraethoxysilane and octamethylcyclotetrasiloxane is formed in the core,
A copolymer c-5 having a core / shell structure in which a copolymer composed of styrene and N, N-diallylformamide was a shell portion was obtained. The copolymer c-5 by IR spectroscopy, formyl group content than the peak intensity of 1600 cm ^-1 and 1660 cm ^-1 was 1.0 wt%.
In addition, 1020~1090cm ^-1 and 1600cm ^-1
From the peak strength of the above, the core portion was 38.5% by weight and the shell portion was 61.5% by weight.

[0108]

Examples 1-28, Comparative Examples 1 and 2, Comparative Examples 1-8
First, (A) shown below other than the component (C),
(B), (D), (E) and (F) components were prepared respectively.

[Component (A)] PC-1: polycarbonate resin (Toughlon A220)
PC-2: Polycarbonate resin (Panlite-L-1)
250, Teijin Chemicals Ltd.)

[Component (B)] HIPS1: Impact-resistant polystyrene (Idemitsu Styrol H)
HIPS2: impact-resistant polystyrene (Sumibright DJ)
HIPS3: Impact-resistant polystyrene (Stylon H86)
52, manufactured by Asahi Kasei Corporation)

[Component (D)] D-1: Halogen-free condensed phosphate ester (CR-7)
D-2: Triphenyl phosphate (TPP, manufactured by Daihachi Chemical Co., Ltd.) D-3: Trixylenyl phosphate (TXP, manufactured by Daihachi Chemical Co., Ltd.)

[Component (E)] PTFE: polytetrafluoroethylene (polyfuron)
MPA FA-500, manufactured by Daikin Chemical Industry Co., Ltd.)

[Component (F)] Silicone: powdered silicone (Si powder DC4
-7105, manufactured by Dow Corning)

The components (A) and (F) shown in Tables 1 and 2 below were mixed in the proportions shown in the same table, and a polycarbonate resin composition was obtained by the following method. That is, Table 1 below
After the components (A) to (F) shown in Table 2 are dry-blended in advance in the proportions shown in the table and dried, the mixture is melt-mixed at 280 ° C. using a twin-screw extruder (KRC kneader, manufactured by Kurimoto Iron Works). Then, pellets of the desired polycarbonate resin composition were obtained. And an injection molding machine (Hipershot 300)
0, manufactured by Niigata Iron Works Co., Ltd.) at 280 ° C. to obtain a molded product.

[0115]

[Table 1]

[0116]

[Table 2]

Using the molded product obtained in this way,
Izod impact strength, weld strength, peelability and flame retardancy were measured and evaluated according to the following evaluation methods, and the results are shown in Tables 3 and 4 below.

[Izod impact strength] JIS-K671
The Izod impact value was measured at 23 ° C. according to No. 9.

[Weld adhesive strength] JIS-K7113
A test piece having the same shape as the No. 2 test piece in the above, injection molded using a mold prepared so that the molten resin is injected from both ends at the time of injection molding and the tip of the molten resin is adhered at the center, and JIS A tensile test was performed according to -K7113.

[Presence or absence of laminar peeling] Evaluation was made based on the peelability by a grid test. That is, a cut is made on the surface of the test piece using a knife, and a 1 mm × 1 mm square 100
The pieces were formed in a grid pattern. Then, a cellophane tape was pressure-bonded to the surface and then peeled off with a strong force, and the number of squares that did not adhere to the cellophane tape and did not peel off from the test piece were counted.

[Flame Retardancy] Measured according to the UL94 standard vertical combustion test (1/8 inch thickness). And V-0
To V-2 satisfy practical combustion performance, and HB means that it has no practical flame retardancy. In addition, in order to examine the error of the test piece, the sum of the burning time after the first flame contact and the burning time after the second flame contact for the polycarbonate resin composition having flame retardancy of V-0 to V-2 was measured. The standard deviation of the burning time was determined.

[0122]

[Table 3]

[0123]

[Table 4]

From the results shown in Tables 3 and 4, among the examples of the polycarbonate resin composition of the present invention, Example 1
No. 14 to No. 14 retained the flame retardancy of V-2 to V-1, were excellent in impact strength and weld strength, had small physical property errors due to molded products, and did not cause delamination. Examples 22 to 25 are polycarbonate resin compositions to which PTFE and silicone, which are optional components, were added, and these were not only excellent in the above-mentioned respective performances, but also improved in the flame retardancy to V-0.

On the other hand, Comparative Examples 1 to 3, which are polycarbonate resin compositions to which the phosphorus-based flame retardant (D) is not added, do not have the desired flame retardancy. Comparative Examples 4 to 8 are the polycarbonate resin compositions to which the component (C) was not added, and the impact strength was greatly reduced and the peelability was poor. In addition, although the flame retardancy achieves V-2 to V-0, the burning time after the first flame contact and the burning time after the second flame contact in the flame retardancy test according to UL94. Is large (especially Comparative Examples 4 to 6), which is an undesirable result as a flame-retardant molding material.

In Comparative Example 1, the impact-resistant polystyrene resin (HIPS) as the component (B) was used more frequently than the preferred mixing ratio. And the standard deviation of the burning time is large. In Comparative Example 2, the phosphorus-based flame retardant as the component (D) was used more frequently than the preferred content, and was better than Comparative Example 1. It is inferior in impact resistance as compared with.

[0127]

As described above, according to the present invention, the resin component (A) and the resin component (B) contain the component (D) as a flame retardant and the resin components (a) to ( c)
A polycarbonate resin composition containing at least one copolymer (component (C)) selected from the group consisting of the above as a compatibilizer for both resins. For this reason, the two resin components are made compatible with each other to provide excellent impact resistance and processing fluidity, reduce physical property errors during molding, prevent the occurrence of delamination, and improve weld adhesion strength and impact resistance. An excellent polycarbonate resin composition having improved properties is obtained.

Further, by using at least one of a polytetrafluoroethylene [(E) component] and a silicone compound [(F) component] together with the above components (A) to (D), more excellent flame retardancy is obtained. Will be given.

Therefore, the polycarbonate resin composition of the present invention is particularly useful, for example, as a molding material for flame-retardant injection molding.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 51/04 C08L 51/04 55/02 55/02 83/04 83/04

Claims (7)

[Claims] 1. A polycarbonate resin composition containing the following components (A) to (D). (A) Polycarbonate resin. (B) Styrene resin. (C) at least one copolymer selected from the group consisting of the following (a) to (c). (A) A copolymer comprising a monomer containing a formamide group-containing monomer represented by the following general formula (1) and an aromatic vinyl monomer as essential components. (B) a copolymer comprising a formamide group-containing monomer represented by the following general formula (1) and a monomer containing at least one of an acrylate monomer and a methacrylate monomer as an essential component; Coalescing. (C) A copolymer having a core / shell structure in which a core is formed of a rubber-like elastic material and a shell covering the core is formed in (a). Embedded image (D) Halogen-free phosphate ester. 2. In the component (C) (a), the proportion of the constituent part derived from the formamide group-containing monomer is 0.05 to 20% by weight, and the proportion derived from the aromatic vinyl monomer is The polycarbonate resin composition according to claim 1, wherein the proportion of the constituent components is set to 60% by weight or more. 3. The acrylate monomer and methacrylate ester according to (b) of component (C), wherein the proportion of the constituent part derived from the formamide group-containing monomer is 0.05 to 20% by weight. 2. The polycarbonate resin composition according to claim 1, wherein the proportion of a component derived from at least one of the monomers is set to 50% by weight or more. 4. The core / shell structure copolymer (c) of the component (C) is a copolymer of a core / shell structure comprising the following core portion (X) and the following shell portion (Y). The polycarbonate resin composition according to claim 1, which is a polymer. (X) A core portion made of the following rubber-like elastic body (x1) or rubber-like elastic body (x2). (X1) The proportion of the constituent component derived from a substance mainly composed of at least one of an acrylate monomer and a methacrylate ester monomer is 50 to 100% by weight, and is represented by the general formula (1). A rubber-like elastic body in which the proportion of a constituent derived from a formamide group-containing monomer is 0 to 20% by weight and the proportion of a constituent derived from a cross-linking component is 0 to 2% by weight. (X2) A rubber-like elastic body in which the proportion of a component derived from a monomer mainly composed of an organosiloxane is 10 to 100% by weight. (Y) The ratio of the constituent part derived from the formamide group-containing monomer represented by the general formula (1) is 0.05 to 20.
A shell portion in which, by weight, the proportion of components derived from the aromatic vinyl monomer is 60% by weight or more. 5. The core / shell structure copolymer (c) of component (C), wherein the core portion is set to 10 to 70% by weight and the shell portion is set to 30 to 90% by weight. The polycarbonate resin composition according to claim 1. 6. The mixing ratio of the component (A) and the component (B) [(A) / (B)] is expressed by a weight ratio of (A) / (B) =
(50 to 90) / (10 to 50), and the content of the component (C) is 0.05 to 100 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). The content of the component (D) is set to 2 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B) in 20 parts by weight. The polycarbonate resin composition according to any one of the above. 7. The method according to claim 1, wherein at least one of the following components (E) and (F) is contained in addition to the components (A) to (D). Polycarbonate resin composition. (E) Polytetrafluoroethylene. (F) a silicone compound.