JP2000319494A - Highly flame-retardant resin composition for thin-wall molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which, when molded, hardly causes mold deposit by compounding a polycarbonate resin with a copolymer containing aromatic vinyl monomer units and vinyl cyanide monomer units, a copolymer formed by grafting an aromatic vinyl monomer component onto a rubbery polymer and an organophosphorus flame retardant. SOLUTION: This composition comprises 70-98 pts.wt. polycarbonate resin, 29-0.1 pt.wt. copolymer containing aromatic vinyl monomer units and vinyl cyanide monomer units; 1-29.9 pts.wt. copolymer prepared by grafting at least one monomer selected from among aromatic vinyl monomers, vinyl cyanide monomers and alkyl (meth)acrylates onto a rubbery polymer (the sum of amounts of ingredients described hereinabove being 100 pts.wt.); and 5-20 pts.wt. flame retardant comprising 99-93 wt.% organophosphorus compound of formula I having an average degree of condensation (N) of 1 or higher but lower than 1.2 and 1-7 wt.% organophosphorus compound of formula II. In the formulas, Ra to Rd are each aryl; (n) is a natural number; X is an aromatic group; Re to Rg are each Ra or the like; (j) to (m) and (q) to (s) are each 0-1; and N is the mean value of (n).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mold deposit generated in a molding die during molding, having high fluidity, high impact resistance and high flame retardancy suitable for thin-wall molding. The present invention relates to a flame-retardant polycarbonate-based resin composition in which the generation amount of (MD) is extremely small.

[0002]

2. Description of the Related Art A resin composition in which an ABS (acrylonitrile / butadiene / styrene) resin and an organic phosphorus flame retardant are blended with polycarbonate (PC) (flame retardant PC / A).
BS alloy) is a non-halogen flame retardant material and has excellent mechanical properties, heat resistance and light resistance, so it is used as a housing material for OA equipment such as electrical products, computers, printers, word processors and copiers. Widely used.

In recent years, there has been a strong demand for lighter and thinner housings for OA equipment, and flame-retardant PC / ABS alloys have been required to have high fluidity, high impact resistance, and thin-walled moldings for thin-wall molding. Therefore, there is a demand for the development of a material that simultaneously satisfies excellent flame retardancy. Techniques relating to a flame-retardant PC / ABS composition in which fluidity, impact resistance and flame retardancy are highly balanced are disclosed in JP-A-6-240127, JP-A-7-82466, and JP-A-8-1276.
No. 86, JP-A-8-25366 and the like.

[0004] The design of a flame-retardant PC / ABS alloy that simultaneously satisfies high fluidity and impact resistance, as well as high flame retardancy, reduces the molecular weight of PC in the composition and increases the composition ratio. The composition composition is becoming mainstream. However, such a composition having a high PC composition is advantageous for improving the flame-retardant performance of the composition, but it is difficult to increase the shear sensitivity (the susceptibility of the decrease in viscosity of the molten resin to an increase in the shear rate). ) In some cases, the fluidity in the high shear speed region required for injection molding may not be sufficiently obtained.

In order to obtain a composition having high fluidity, it is desirable that the organophosphorus flame retardant used has a low viscosity. In particular, when the composition ratio of PC in the composition is high, the viscosity of the organic phosphorus-based flame retardant itself greatly affects the fluidity of the composition. For this reason, when a mono-organic phosphorus compound having a lower viscosity than the oligomer-based organic phosphorus compound is used as a flame retardant, the viscosity in a high shear rate region is low, that is, a high-flow resin composition suitable for thin-wall molding. Is convenient for the purpose of obtaining However, when a mono-organic phosphorus compound is used as a flame retardant, there is a drawback that a large amount of MD adheres to the mold surface during molding. JP-A-7-82466 and JP-A-8-253
No. 66 discloses a composition in which an oligomeric organic phosphorus compound and a mono-organic phosphorus compound are used in combination as an organic phosphorus-based flame retardant. M sometimes adheres to the mold surface
The amount of D generated is still large, and its improvement is desired.

As described above, a non-halogen flame-retardant material which is suitable for thin-wall molding, has high flow resistance, has excellent impact resistance and high flame-retardant performance, and has a low MD during molding. In spite of the demand for a material, a material satisfying all these properties has not yet been obtained.

[0007]

SUMMARY OF THE INVENTION Accordingly, the present invention is directed to an MD having high fluidity, high impact resistance and high flame retardancy suitable for thin-wall molding, and which adheres to a molding die during molding. It is an object of the present invention to provide a flame-retardant polycarbonate-based resin composition in which the generation amount of resin is extremely small.

[0008]

Means for Solving the Problems The present inventors controlled the average degree of condensation N of the oligomeric organophosphorus compound as a flame retardant to 1 or more and less than 1.2, and furthermore, based on the total amount of the organophosphorus flame retardant. By using a combination of several wt% of mono-organic phosphorus compound, it is found that a composition having high flame retardancy and excellent fluidity and shear sensitivity can be obtained,
Furthermore, it was found that when a small amount of a mono-organic phosphorus compound was blended, the amount of MD generated in a molding die during molding was extremely low, and the present invention was achieved.

That is, the present invention provides [1] (A) 70 to 98 parts by weight of a polycarbonate resin having a weight average molecular weight (Mw) of 15,000 to 25,000, (B) a weight average molecular weight (Mw) of 50, 29 to 0.1 parts by weight of a copolymer containing (b1) an aromatic vinyl monomer component of not less than 000 and 150,000 or less, and (b2) a vinyl cyanide monomer component, (C) (c1) aromatic Vinyl monomer component, (c
2) at least one of a vinyl cyanide monomer component and (c3) an alkyl (meth) acrylate monomer component
One or more of (c4) contains 1 to 29.9 parts by weight of a copolymer obtained by graft-polymerizing a rubbery polymer, and further contains (A), (B), and (C) in a total of 100 parts by weight. On the other hand, (D) (d1) 99 to 93 wt% of one or more oligomeric organophosphorus compounds represented by the formula (1) having an average condensation degree N of 1 or more and less than 1.2; ) Organophosphorus compound comprising a combination of 1 to 7 wt% of one or more mono-based organophosphorus compounds represented by formula (2) (provided that the sum of (d1) and (d2) is 100 wt%) 5 to 20 parts by weight of a flame-retardant resin composition,

[0010]

Embedded image

[0011]

Embedded image

[2] The flame-retardant resin composition according to the above-mentioned [1], wherein (d1) of the component (D) is one or more oligomeric organic phosphorus compounds represented by the formula (3):

[0013]

Embedded image

[3] In the formula (3), the substituent R ^a ,
The flame-retardant resin composition according to the above [2], wherein R ^b , R ^c , and R ^d are all oligomeric organophosphorus compounds, wherein [4] the component (C) is (c1) an aromatic vinyl monomer Monomer component and (c2) vinyl cyanide monomer component
4) a copolymer graft-polymerized to a rubbery polymer;
(C3) The above-mentioned [1], wherein the alkyl (meth) acrylate monomer component comprises a combination of a copolymer obtained by graft-polymerizing the (c4) rubbery polymer.
[2] and the flame-retardant resin composition according to [3], [5] above [1] further containing polytetrafluoroethylene,
A flame-retardant resin composition according to [2], [3] or [4].

Hereinafter, the present invention will be described in detail. The polycarbonate resin (A) used in the present invention has the formula (4)
Having a main chain consisting of a repeating unit represented by

[0016]

Embedded image

(In the formula, Ar is a divalent aromatic residue, for example, phenylene, naphthylene, biphenylene,
Examples include pyridylene and those represented by the formula (5). )

[0018]

Embedded image

(In the formula, Ar ¹ and Ar ² are each an arylene group. For example, they represent groups such as phenylene, naphthylene, biphenylene, and pyridylene, and Y represents an alkylene group or a substituted alkylene group represented by the formula (6). Is.)

[0020]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a lower alkyl group, a cycloalkyl group,
An aryl group or an aralkyl group, which may be optionally substituted by a halogen atom or an alkoxy group;
And R ⁵ and R ⁶ are independently selected for each X, and each independently represents a hydrogen atom, or a lower alkyl group or an aryl group, and is optionally substituted with a halogen atom or an alkoxy group. And X represents a carbon atom. ) Further, a divalent aromatic residue represented by the formula (7) may be contained as a copolymer component.

[0022]

Embedded image

(Wherein Ar ¹ and Ar ² are the same as in the formula (4).
Z is a mere bond, or -O-, -CO-, -S-,
_{-SO 2 -, - CO 2 -} , - CON (R 1) - (R 1 is as defined in the formula (6)) is a divalent group such as. Examples of these divalent aromatic residues include those represented by formulas (8) and (9).

[0024]

Embedded image

[0025]

Embedded image

(Wherein R ⁷ and R ⁸ are each independently:
Hydrogen, halogen, C ₁ -C ₁₀ alkyl group, C ₁ -C ₁₀ alkoxy group, C ₁ -C ₁₀ cycloalkyl group or a phenyl group. m and n are integers of 1 to 4; when m is 2 to 4, each R ⁷ may be the same or different; and when n is 2 to 4, each R ⁸ is the same. However, they may be different. Among them, one represented by the formula (10) is a preferable example. In particular, a compound containing 85 mol% or more of a repeating unit in which the compound represented by the formula (10) is Ar is preferable.

[0027]

Embedded image

The polycarbonate that can be used in the present invention may contain a trivalent or higher aromatic residue as a copolymer component. Although the molecular structure of the polymer terminal is not particularly limited, one or more terminal groups selected from a phenolic hydroxyl group, an aryl carbonate group, and an alkyl carbonate group can be bonded. The aryl carbonate terminal group is represented by the formula (11), and specific examples include:
For example, equation (12) is given.

[0029]

Embedded image

(In the formula, Ar ³ is a monovalent aromatic residue, and the aromatic ring may be substituted.)

[0031]

Embedded image

The alkyl carbonate terminal group has the formula (13)
And a specific example is, for example, the formula (14).

[0033]

Embedded image

(Wherein, R ⁷ represents a linear or branched alkyl group having 1 to 20 carbon atoms)

[0035]

Embedded image

Of these, phenolic hydroxyl group, phenyl carbonate group, pt-butylphenyl carbonate group, p-cumylphenyl carbonate and the like are preferably used. In the present application, the ratio of the phenolic hydroxyl group terminal to the other terminal is not particularly limited, but the phenolic hydroxyl group terminal ratio for all terminals is preferably in the range of 20 to 80 mol%.

The method for measuring the amount of phenolic hydroxyl group terminals is as follows:
In general, a method using NMR, a titanium method,
It can be determined by the V or IR method. The weight average molecular weight (Mw) of the polycarbonate resin (A) used in the present invention is in the range of 15,000 to 25,000. It is preferably from 17,000 to 24,000, more preferably from 18,000 to 230,000,
Particularly preferably, it is 18,500-22,000. 1
If it is less than 5,000, the impact resistance is insufficient.
If it exceeds 5,000, it is difficult to obtain a high-flow composition intended for the present invention.

The measurement of the weight average molecular weight (Mw) in the present invention is carried out using gel permeation chromatography (GPC). The measurement conditions are as follows: tetrahydrofuran is used as a solvent, and polystyrene gel is used.
It is determined from the constitutive curve of the standard monodisperse polystyrene using a reduced molecular weight calibration curve according to the following equation. ^{_{M PC = 0.3591M PS 1.0388 (M}} PC molecular weight of the polycarbonate, M _PS molecular weight of polystyrene) These polycarbonates can be prepared by known methods. Specifically, a known method of reacting an aromatic dihydroxy compound with a carbonate precursor, for example,
Interfacial polymerization method (phosgene method) in which aromatic dihydroxy compound and phosgene react in the presence of sodium hydroxide aqueous solution and methylene chloride solvent, transesterification method in which aromatic dihydroxy compound reacts with diphenyl carbonate (melting method), crystallization carbonate Method for solid-state polymerization of prepolymer (JP-A-1-158033, 1-27142)
6, 3-68627, etc.).

Preferred polycarbonate resins include:
A polycarbonate resin containing substantially no chlorine atom, which is produced from a dihydric phenol (aromatic dihydroxy compound) and a carbonic acid diester by a transesterification method, may be mentioned. In the present invention, two or more types of components (A) having different structures and molecular weights can be used in combination.

The proportion of the component (A) for obtaining a resin composition in which fluidity, impact resistance and flame retardancy are balanced at a high level, which is the object of the present invention, is as follows: (A) and (B) 70 parts by weight to 98 parts by weight, preferably 75 to 95 parts by weight, more preferably 78 to 9 parts by weight, based on 100 parts by weight in total of (C).
0 parts by weight. When the amount of the component (A) is less than 70 parts by weight, heat resistance and flame retardancy are insufficient, while when it exceeds 98 parts by weight, fluidity is insufficient.

The component (B) used in the present invention comprises (b)
1) A copolymer containing an aromatic vinyl monomer component and (b2) a vinyl cyanide monomer component. The fluidity of the resin composition can be improved by the component (B). Here, as the aromatic vinyl monomer component (b1), for example, styrene, α-methylstyrene, paramethylstyrene, vinylxylene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene and the like can be mentioned. These are used alone or in combination of two or more. Preferred are styrene and α-methylstyrene.

The vinyl cyanide monomer component (b2) includes, for example, acrylonitrile, methacrylonitrile and the like, and one or more of these are used. The composition ratio of (b1) / (b2) in the copolymer is not particularly limited, but preferably (b1) is 95 to 5
0% by weight, (b2) is 5 to 50% by weight, more preferably (b1) is 92 to 65% by weight, and (b2) is 8 to 50% by weight.
35% by weight.

In the component (B), in addition to the components (b1) and (b2), a monomer copolymerizable with these components may be used as long as the gist of the present invention is not hindered. Can be. Such copolymerizable monomers include,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, 2-ethyl (meth) acrylate, 2-
Alkyl (meth) acrylate monomer components such as ethylhexyl methacrylate, preferably butyl acrylate,
(Meth) acrylic acids such as acrylic acid and methacrylic acid, α, β-unsaturated carboxylic acids such as maleic anhydride, N
Maleimide monomers such as -phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide; and glycidyl group-containing monomers such as glycidyl methacrylate. These monomers may be used alone or in combination of two or more. Can be used.

Preferred examples of the component (B) include styrene-acrylonitrile copolymer resin (SAN) and butyl acrylate-styrene-acrylonitrile copolymer resin (BAAS).
(Preferably the butyl acrylate monomer component is 2 to 20
% By weight) is particularly suitable for improving the flowability of the resin composition.

Examples of the method for producing the component (B) include generally known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The weight average molecular weight (Mw) of component (B) is in the range of 50,000 to 150,000. It is preferably from 60,000 to 140,000, more preferably from 70,000 to 130,000, and particularly preferably from 80,000 to 120,000. If it is less than 50,000, the impact resistance is insufficient,
If it exceeds 150,000, it is difficult to obtain a highly fluid composition.

Component (B) for achieving the object of the present invention
Is 29 parts by weight to 0.1 part by weight, preferably 20 parts by weight, based on 100 parts by weight in total of (A), (B) and (C).
1 part by weight, more preferably 15 to 3 parts by weight. If the component (B) is less than 0.1 part by weight, the fluidity becomes insufficient,
On the other hand, when it exceeds 29 parts by weight, heat resistance and flame retardancy are insufficient. Component (B) can be used in combination of two or more components (B) having different structures and molecular weights.

Next, the component (C) will be described. (C) is at least one or two of (c1) an aromatic vinyl monomer component, (c2) a vinyl cyanide monomer component, and (c3) an alkyl (meth) acrylate monomer component.
At least one kind is a copolymer obtained by graft-polymerizing the (c4) rubbery polymer. Examples of the (c1) aromatic vinyl monomer component and (c2) vinyl cyanide monomer component include (b1) and (b2) shown in the component (B).

The (c3) alkyl (meth) acrylate monomer component includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Alkyl (meth) acrylate monomers such as ethyl (meth) acrylate and 2-ethylhexyl methacrylate can be used, and one or more of these are used. Preferred is methyl methacrylate.

As the rubbery polymer (c4), those having a glass transition temperature of 0 ° C. or lower can be used. Specifically, polybutadiene, styrene-butadiene copolymer rubber, diene rubber such as acrylonitrile-butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, polyisoprene, polychloroprene, ethylene propylene rubber, ethylene propylene rubber・ Including block copolymers such as diene terpolymer rubber, styrene / butadiene block copolymer rubber, styrene / isoprene block copolymer rubber and their hydrogenated products, polyorganosiloxane component and polyalkyl (meth) acrylate component Composite rubber (silicone-acrylic composite rubber) or the like can be used. Among these polymers, preferred are polybutadiene, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, polybutyl acrylate, and silicone / acryl composite rubber.

The component (C) is obtained by adding (c1) an aromatic vinyl monomer component, (c2) a vinyl cyanide monomer component, and (c3) an alkyl (meth) to the (c4) rubbery polymer.
At least one or two or more of the acrylate monomer components may further include, if necessary, (meth) acrylic acids such as acrylic acid and methacrylic acid, α, β-unsaturated carboxylic acids such as maleic anhydride, Bulk polymerization, suspension polymerization, bulk / suspension of one or more maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, and glycidyl group-containing monomer components such as glycidyl methacrylate It is obtained by graft polymerization using a method such as polymerization, solution polymerization or emulsion polymerization, particularly emulsion polymerization.

Here, the amount of the rubbery polymer (c4) used is usually from 10 to 95% by weight, preferably from 30 to 82% by weight, more preferably from 40 to 80% by weight. When a butadiene-based polymer is used, the ratio of the butadiene component of the butadiene-based polymer is preferably 50% by weight or more. If the amount of the rubbery polymer in the component (C) is less than 10% by weight, the effect of improving the impact resistance is low, and
If the content is more than 10% by weight, the dispersion of the component (C) in the composition becomes insufficient, which is not preferable.

In the present invention, a particulate graft copolymer obtained by emulsion polymerization can be most preferably used as the component (C). In this case, the average particle size of the graft copolymer is It is preferably from 0.1 to 1.5 μm, more preferably from 0.15 to 0.8 μm, particularly preferably from 0.2 to 0.6 μm. When the thickness is less than 0.1 μm, the effect of improving the impact resistance of the resin composition is insufficient, and
If it exceeds m, the fluidity and the appearance of the molded article will deteriorate.

Preferred examples of the component (C) according to the present invention include acrylonitrile / butadiene / styrene copolymer, acrylonitrile / ethylene / propylene / styrene copolymer, acrylonitrile / chlorinated polyethylene / styrene copolymer, acrylonitrile / acrylic Elastic polymer / styrene copolymer. Further, in the present invention, as the component (C), a copolymer obtained by grafting only the (c3) alkyl (meth) acrylate monomer component to the (c4) rubbery polymer is used, which has high fluidity and impact resistance. It is more preferable to balance the properties at a high level, and a copolymer in which methyl methacrylate is grafted as the component (c3) is particularly preferable. As such an example, a styrene-butadiene-methyl methacrylate copolymer or a copolymer obtained by grafting methyl methacrylate onto silicon-acrylic rubber can be suitably used. For example, it is manufactured by Mitsubishi Rayon Co., Ltd. ,
“METABLEN C-233A”, “METABLEN C-3”
23A "and" METABLEN S-2001 "(both are trade names) are particularly preferably used.

In the resin composition of the present invention, the above component (C)
Can be used alone or in combination of two or more. The compounding amount is 1 part by weight to 29.9 parts by weight with respect to 100 parts by weight in total of (A), (B) and (C). It is. Preferably from 2 to 20 parts by weight, more preferably from 3 to
15 parts by weight. If the amount of the component (C) is less than 1 part by weight, there is almost no effect of improving impact resistance, while if it exceeds 29.9 parts by weight, fluidity and rigidity are insufficient.

In particular, in the composition of the present invention, as the component (C), a copolymer obtained by graft-polymerizing an aromatic vinyl monomer component and a vinyl cyanide monomer component onto a rubbery polymer, for example, acrylonitrile. A butadiene / styrene copolymer (hereinafter referred to as C (a) component) and a copolymer obtained by graft-polymerizing methyl methacrylate on a rubbery polymer;
For example, by using a styrene-butadiene-methyl methacrylate copolymer or a copolymer obtained by grafting methyl methacrylate onto silicon-acrylic rubber (hereinafter referred to as C (b) component), fluidity and impact resistance are improved. It is suitable for obtaining a resin composition balanced at a high level. In this case, the composition ratio of C (a) and C (b) is not particularly limited, but the C (b) component is preferably 90 to 10% by weight, more preferably the total amount of C (a) and C (b). Is 70 to 20% by weight, more preferably 60 to 3% by weight.
0 wt%.

The component (D) used in the present invention comprises (d)
1) 99 to 93 wt% of one or more oligomeric organic phosphorus compounds represented by the formula (1) having an average degree of condensation N of 1 or more and less than 1.2, and (d2) a formula represented by the formula (2). 1 to 7 wt. Of one or more mono-organic phosphorus compounds
% (However, the sum of (d1) and (d2) is 100 wt%
) Of the organic phosphorus compound.

[0057]

Embedded image

[0058]

Embedded image

The component (d1) is represented by the formula (1), and the substituents R ^a , R ^b , R ^c , and R ^d in the formula (1) are aryl groups, and one or more hydrogens thereof are substituted. You don't have to. Compounds in which the substituents R ^a , R ^b , R ^c , and R ^d are an alkyl group or a cycloalkyl group have insufficient retention stability of the molten resin in a molding machine during injection molding, resulting in a decrease in physical properties of the resin. Easy to invite. When one or more hydrogens of the substituents R ^a , R ^b , R ^c , and R ^d are substituted, the substituent may be an alkyl group, an alkoxy group, an alkylthio group, a halogen,
Examples include an aryl group, an aryloxy group, an arylthio group, and a halogenated aryl group. A group obtained by combining these substituents (for example, an arylalkoxyalkyl group) or these substituents are replaced with an oxygen atom, a sulfur atom, a nitrogen atom A group (for example, an arylsulfonylaryl group or the like) combined by bonding through the above may be used as a substituent. Preferred aryl groups are phenyl, cresyl,
Xylyl group, propylphenyl group and butylphenyl group, and phenyl group is particularly excellent in both fluidity and flame retardancy. Further, the substituents R ^a , R ^b , R ^c , and R ^d may be the same or different.

X in the formula (1) is an aromatic group derived from a dihydric phenol, and catechol,
Resorcinol, hydroquinol, 4-t-butylcatechol, 2-t-butylhydroquinone, bisphenol A, bisphenol S sulfide, bisphenol F,
Bis (4-hydroxyphenyl) sulfone, bis (3
An aromatic group derived from (5dimethyl-4-hydroxyphenyl) sulfone and the like can be mentioned, and in the present invention, the compound represented by the formula (3)

[0061]

Embedded image

X is a diphenyloldimethylmethane group (an aromatic group derived from bisphenol A)
By using the oligomeric organophosphorus compound, the retention stability can be improved and the generation of MD can be reduced. The oligomeric organic phosphorus compounds represented by the formulas (1) and (3) are usually used as a mixture of compounds having different values of n (n is a natural number) in the formulas (1) and (3). Often. The average degree of condensation N is the average value of n. N is calculated by calculating the weight fraction of each component having different n by gel permeation chromatography and calculating the weight average of n. The detector is R
Use an I detector. However, in the present invention, a component in which n is 0, that is, a compound having only one phosphorus atom in the molecule is excluded from the calculation of N.

In the present invention, the average value N (average degree of condensation) of n is 1 or more and less than 1.2. The smaller the N, the better the compatibility with the resin, the better the fluidity, and the higher the flame retardancy. In particular, N
The compound of = 1 is particularly excellent in the balance between flame retardancy and fluidity in the resin composition. When N is 1.2 or more, the viscosity increases, and it becomes difficult to obtain a highly fluid composition, particularly a composition having excellent fluidity in a high shear rate region, and the flame retardancy is reduced. .

The oligomeric organophosphorus compound according to the present invention is characterized in that N is at least 1 and less than 1.2. A method for obtaining such an oligomeric organophosphorus compound having a small N is, for example, as follows. [A] Phosphorus oxyhalide is reacted with an aromatic monohydroxy compound such as phenol or 2,6-xylenol under a Lewis acid catalyst to obtain a diaryl phosphorohalide in advance, followed by bisphenol A, A method obtained by reacting an aromatic dihydroxy compound (a dihydric phenol compound) such as hydroquinone or resorcinol under a Lewis acid catalyst. [A] An aromatic dihydroxy compound is reacted with a large excess thereof (about 4 times molar equivalent or more) of phosphorus oxyhalide under a Lewis acid catalyst, and then the excess phosphorus oxyhalide is completely removed by heating under reduced pressure. And then reacting the reaction product with an aromatic monohydroxy compound in the presence of a Lewis acid catalyst. And the like.

The component (d2) is represented by the formula (2), and the substituents R ^e , R ^f and R ^g in the mono-organic phosphorus compound represented by the formula (2) are each independently represented by the formula (1) )), And the aromatic groups derived from dihydric phenols, in addition to those represented by the substituents R ^a , R ^b , R ^c and R ^d . Specific examples of preferred mono-organic phosphorus compounds include triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, trixylenyl phosphate, xylenyl phenyl phosphate, and the like.

The component (d2) is composed of a fluid shear
It has the effect of improving sensitivity, and has a content of 1 to 7% by weight, preferably 2 to 6% by weight, based on the total amount of the component (D).
More preferably, 3 to 5 wt% is contained. If it is less than 1 wt%, the effect of improving the shear sensitivity is insufficient, while if it exceeds 7 wt%, the amount of MD generated increases.

As the component (d2), a predetermined amount is blended and melt kneading is carried out. Alternatively, the by-produced mono-organic phosphorus compound contained in the oligomer-type organic phosphorus compound may be used as it is. When the method [1] is used as a method for producing an oligomeric organic phosphorus compound, the content of the mono-organic phosphorus compound by-produced can be controlled by the production conditions.

The content of the organic phosphorus compound (D) in the composition is 5 to 20 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C). If it is less than 5 parts by weight, the flame retardant effect is insufficient. On the other hand, if it exceeds 20 parts by weight, the impact resistance and heat resistance of the resin composition decrease. Preferably 8 to
The range is 17 parts by weight, and a particularly preferred range is 10 to 10 parts by weight.
It is in the range of 15 parts by weight.

Further, it is effective and preferable to use an anti-dripping agent in combination with the component (D). Examples of the anti-dripping agent include perfluoroalkane polymers such as polytetrafluoroethylene, silicone rubber, polycarbonate / diorganosiloxane copolymer, siloxane polyetherimide, liquid crystal polymer, and the aforementioned silicone / acryl composite rubber. Particularly preferred is polytetrafluoroethylene, which is preferably in the range of 0.01 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, when the total of components (A) to (C) is 100 parts by weight. Department. If the amount is less than 0.01 part by weight, the effect of preventing dripping during combustion is insufficient, and high flame retardancy cannot be obtained. Also, 3
When the amount is more than the weight part, the moldability and rigidity are reduced.

Further, in combination with the component (D), other flame retardants other than the component (D), for example, nitrogen-containing organic compounds such as melamine, inorganic compounds such as magnesium hydroxide and aluminum hydroxide, antimony oxide, oxides Metal oxides such as bismuth, zinc oxide and tin oxide, red phosphorus, phosphine, hypophosphorous acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, inorganic phosphorous compounds such as phosphoric anhydride, expanded graphite, silica, silica-based A glass melt or the like may be contained within a range not contrary to the gist of the present invention.

The method for producing the resin composition of the present invention is not particularly limited, and the resin composition can be produced by a usual method, for example, melt blending by extrusion kneading. Further, the molding method of molded articles made of these thermoplastic resin compositions includes extrusion molding, compression molding, injection molding,
There is gas assist molding or the like, and there is no particular limitation.

[0072]

The present invention will be described in detail with reference to the following examples. The materials used are shown below. 1. (A) Component (Polycarbonate: PC1) Bisphenol A-based polycarbonate (Polycarbonate: PC2) molten ester having a Mw of 20,000 and a hydroxyl group terminal amount of 33% produced from bisphenol A and diphenyl carbonate by a melt transesterification method. 1. Bisphenol A-based polycarbonate having an Mw of 26,000 and a hydroxyl group terminal content of 30% produced by an exchange method. (B) Component (Acrylonitrile / styrene copolymer: SAN1) Acrylonitrile unit 25.0 wt%, styrene unit 7
Acrylonitrile / styrene copolymer composed of 5.0 wt% and having Mw of 140,000 (acrylonitrile / styrene copolymer: SAN2) 29.0 wt% of acrylonitrile unit, 7 of styrene unit
Acrylonitrile-styrene copolymer (butyl acrylate-acrylonitrile-styrene copolymer: BAAS) composed of 1.0 wt% and having a Mw of 180,000 butyl acrylate unit 10.0 w
2. A butyl acrylate / acrylonitrile / styrene copolymer having a Mw of 110,000, which is composed of at%, acrylonitrile unit 27.0 wt%, and styrene unit 63.0 wt%. (C) Component (Acrylonitrile / Butadiene / Styrene Copolymer Rubber: ABS) Powdered ABS resin having a mesh residue of less than 90% (manufactured by Mitsubishi Rayon Co., Ltd., trade name RC) (Methyl methacrylate / styrene) -Butadiene copolymer rubber: MBS) Methyl methacrylate grafted styrene / butadiene rubber (Metrene C-233A (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) whose outermost layer is coated with methyl methacrylate) (Methyl methacrylate grafted silicone acrylic rubber: Silicone rubber composite rubber) Composite rubber (manufactured by Mitsubishi Rayon Co., Ltd.) in which a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component whose outermost layers are coated with methyl methacrylate have a mutual intrusion network structure. METABLEN S-20 1) 4. (D) Component (Organic phosphorus compound (D1)) Organophosphorus compound obtained by the method of Reference Example 1 below. (Reference Example 1) Bisphenol A (30 liter container) equipped with an agitator, a condenser, and a heating jacket 1 mole equivalent) to phosphorus oxychloride (5
Molar equivalent) and magnesium chloride (0.025 molar equivalent)
, And the mixture was gradually heated and stirred, heated to 120 ° C., and further reacted for 7 hours. Hydrochloric acid by-produced in the reaction is led to a hydrochloric acid absorption tower. Phosphorus oxychloride was removed from the obtained reaction mixture under reduced pressure at 160 ° C. and 1 mmHg for 4 hours. Thereafter, phenol (4.5 mol equivalent) was gradually added with stirring, and the reaction was completed at 150 ° C. for 8 hours to complete the reaction. After completion of the reaction, the remaining phenol was removed from the reaction mixture under reduced pressure at 170 ° C. and 20 mmHg for 3 hours, and the obtained product was washed and dried. Then, the remaining phenol was completely removed by a thin film distillation method. An oligomeric organic phosphorus compound represented by the formula (15) was obtained. The average degree of condensation N and the content (wt%) of the mono-organic phosphorus compound in the product were determined by GPC measurement to be 1.12 and 0.8 wt%, respectively.

[0073]

Embedded image

(Organic phosphorus compound (D2)) Referential Example 2 below
(Reference Example 2) Phosphorus oxychloride (1.5 mole equivalent) and magnesium chloride (0.025 mole) were used in the autoclave used in Example 1 with respect to bisphenol A (1 mole equivalent) in the autoclave used in Example 1. (Molar equivalent), and the mixture was gradually heated and stirred, heated to 120 ° C., and further reacted for 7 hours. Hydrochloric acid by-produced in the reaction is led to a hydrochloric acid absorption tower. Phosphorus oxychloride was removed from the obtained reaction mixture under reduced pressure at 120 ° C. and 30 mmHg for 2 hours. Thereafter, phenol (4.5 mol equivalent) was gradually added with stirring, and the reaction was completed at 150 ° C. for 8 hours to complete the reaction. After completion of the reaction, the remaining phenol was removed from the reaction mixture under reduced pressure at 170 ° C. and 20 mmHg for 3 hours, and the obtained product was washed and dried. Then, the remaining phenol was completely removed by a thin film distillation method. An oligomeric organic phosphorus compound represented by the formula (15) was obtained. The average degree of condensation N of the obtained phosphorus compound and the content (wt%) of the mono-organic phosphorus compound in the product were 2.12 and 3.5 wt%, respectively. (Organic phosphorus compound (D3)) Product name PX-200 manufactured by Daihachi Chemical Industry Co., Ltd. Formula (16) in which the average degree of condensation N is 1.00 and the content of the mono-organic phosphorus compound is 0.4 wt%. Oligomeric organophosphorus compounds

[0075]

Embedded image

(Organic phosphorus compound (D4)) Triphenyl phosphate (TPP) manufactured by Daihachi Chemical Industry Co., Ltd. (Organic phosphorus compound (D5)) The average degree of condensation N is 1.13.
Oligomeric organophosphorus compound represented by the following formula (17) having a content of mono-based organophosphorus compound of 3.5 wt%

[0077]

Embedded image

5. Other components (Fluorine-based resin: PTFE) Product name: Teflon 3 manufactured by Mitsui Dupont Fluorochemicals
0J Polytetrafluoroethylene Aqueous Dispersion Each test in Examples and Comparative Examples was performed by the following methods. (1) Flame retardancy test The obtained pellets were dried, and the cylinder temperature was 250 ° C.
Molding was performed with an injection molding machine (Autoshot 50D, manufactured by FANUC) set at a mold temperature of 65 ° C. to prepare a test piece shaped body for a combustion test. The flame retardancy was evaluated based on the UL94 standard vertical combustion test (UL94). (2) Measured at 220 ° C. under a load of 10 kg according to MFR ASTM D1238. (Unit: g / 10 min) (3) Shear sensitivity evaluation of melt viscosity According to Capillograph manufactured by Toyo Seiki Co., Ltd., the capillary length is 10.0 mm, the capillary diameter is 1.00 mm, and the measurement temperature is 260 ° C. The properties were measured.
The composition's shear sensitivity is evaluated as follows. That is, a shear speed of 122 / s and 2,432
/ S is η (122), η (2,4
32), η (122) / η (2,432)
Is defined as the η ratio, and the evaluation is made based on the value of the η ratio. When the η ratio is large, it indicates that the fluidity is excellent in a high shear velocity region. (4) Izod impact test A 1/8 inch, notched measurement was made according to ASTM D256. (Unit: kgf · cm / cm) (5) Evaluation of mold deposit (MD) Injection pressure was 905 kgf / cm ² using an injection molding machine (NIIGATA CN75) set at a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C. Under the conditions of a time of 3 seconds, a cooling time of 1.2 seconds, a pause time of 2 seconds, and a molding cycle of 8.3 seconds, a molded body having a test piece weight of 4 g was continuously molded.
The surface state of the mold after 00 and 1,000 shots was visually observed. ：: No MD was observed at 1,000 shots. Δ: MD is observed in 500 shots or less. X: MD is observed in 100 shots or less.

[0079]

Examples 1 and 2 and Comparative Examples 1 to 4 The resin compositions were blended in the composition (parts by weight) shown in Table 1 and a twin-screw extruder (ZSK-25,
(W & P) to obtain pellets of the resin composition. The oligomeric phosphorus compound was compounded by press-fitting the middle stage of the extruder with a gear pump. The obtained pellets were dried, and the MFR and the melt viscosity were measured for the shear speed dependence. Examined. Example 1 shows that the shear sensitivity is improved by the addition of the mono-organic phosphorus compound, as compared with Comparative Example 1. Incidentally, the spiral flow length (thickness 2 mm, width 6 mm) of the composition of Example 1 and the composition of Comparative Example 2 was measured at an injection temperature of 260.
° C, injection pressure 1,500 kgf / cm ² , injection speed 200
When measured under the condition of mm / s, Example 1 (η ratio was 3.85) was 53 cm, and Comparative Example 1 (η ratio was 3.2).
5) was 47 cm. Comparative Example 2 is a case where the average degree of condensation N of the oligomeric organophosphorus compound is out of the range of the present invention, but the shear sensitivity is inferior to that of Example 1, and the flame retardant level is lowered. In Comparative Example 3, occurrence of MD is observed. Comparative Example 4 is lower in shear sensitivity and flame retardant level than Example 2.

[0080]

Examples 3-6, Comparative Examples 5-7 The resin compositions were blended in the compositions (parts by weight) shown in Table 2 to obtain pellets of the resin compositions in the same manner as in Example 1. When the oligomeric organic phosphorus compound was in a liquid state, the oligomeric organic phosphorus compound was compounded by press-fitting with a gear pump in the middle stage of the extruder.

The obtained pellets were dried, the cylinder temperature was set at 260 ° C., and the mold temperature was set at 65 ° C., and they were molded by an injection molding machine, and various evaluations were made. Table 2 shows the results. It can be seen that all of Examples 3 to 6 are simultaneously excellent in fluidity, impact resistance, flame retardancy, and low MD property. Comparative Example 5 is a result in which the molecular weight of PC is out of the range of the present invention, and the fluidity is poor. In Comparative Example 6, the composition ratio of PC was out of the range of the present invention, and the flame retardancy was poor. In Comparative Example 7, the SAN had a molecular weight outside the range of the present invention, and was inferior in fluidity.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

As described above, the present invention has high fluidity, high impact resistance and high flame retardancy suitable for thin-wall molding, and at the same time, it is generated in the molding die during molding. It is possible to provide a flame-retardant polycarbonate-based resin composition in which the amount of generated mold deposits (MD) is extremely small.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 28, 1999 (1999.5.2
8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

(Organic phosphorus compound (D2)) Referential Example 2 below
(Reference Example 2) Phosphorous oxychloride (1.5 mol equivalent) and magnesium chloride (0.025 mol) were used in the autoclave used in Example 1 with respect to bisphenol A (1 mol equivalent) in the autoclave used in Example 1. (Molar equivalent), and the mixture was gradually heated and stirred, heated to 120 ° C., and further reacted for 7 hours. Hydrochloric acid by-produced in the reaction is led to a hydrochloric acid absorption tower. Phosphorus oxychloride was removed from the obtained reaction mixture under reduced pressure at 120 ° C. and 30 mmHg for 2 hours. Thereafter, phenol (4.5 mol equivalent) was gradually added with stirring, and the reaction was completed at 150 ° C. for 8 hours to complete the reaction. After completion of the reaction, the remaining phenol was removed from the reaction mixture under reduced pressure at 170 ° C. and 20 mmHg for 3 hours. The obtained product was washed and dried, and the remaining phenol was completely removed by a thin film distillation method. An oligomeric organic phosphorus compound represented by the formula (15) was obtained. The average degree of condensation N of the obtained phosphorus compound and the content (wt%) of the mono-organic phosphorus compound in the product were 2.12 and 3.5 wt%, respectively. (Organic phosphorus compound (D3)) Product name PX-200 manufactured by Daihachi Chemical Industry Co., Ltd. Formula (16) in which the average degree of condensation N is 1.00 and the content of the mono-organic phosphorus compound is 3.2 wt%. Oligomeric organophosphorus compounds represented

Claims (5)

[Claims] (A) a weight average molecular weight (Mw) of 15,
2,000 to 25,000 polycarbonate resin 7
0 to 98 parts by weight, (B) the weight average molecular weight (Mw) is 5
29 to 0.1 parts by weight of a copolymer containing (b1) an aromatic vinyl monomer component in an amount of from 0000 to 150,000 and (b2) a vinyl cyanide monomer component, (C) (c1)
At least one or more of the aromatic vinyl monomer component, (c2) vinyl cyanide monomer component, and (c3) alkyl (meth) acrylate monomer component are (c4) a rubbery polymer Copolymer 1 graft-polymerized
２９29.9 parts by weight, and (D) (d1) the average degree of condensation N is 1 or more and less than 1.2 based on 100 parts by weight in total of (A), (B) and (C). One or more oligomeric organophosphorus compounds represented by the formula (1) 9
9 to 93 wt% and (d2) 1 to 7 wt% of one or more mono-organic phosphorus compounds represented by the formula (2) (provided that the total of (d1) and (d2) is 100 wt%) A) a flame-retardant resin composition comprising 5 to 20 parts by weight of an organic phosphorus compound comprising the combination of Embedded image Embedded image 2. The flame-retardant resin composition according to claim 1, wherein (d1) of component (D) is one or more oligomeric organic phosphorus compounds represented by formula (3). Embedded image 3. In the formula (3), substituents R ^a , R ^b , R
3. The flame-retardant resin composition according to claim 2, wherein ^c and R ^d are each an oligomeric organic phosphorus compound having a phenyl group. 4. A copolymer obtained by graft-polymerizing (c) a component (c1) an aromatic vinyl monomer component and (c2) a vinyl cyanide monomer component onto (c4) a rubbery polymer; 4. The flame-retardant resin according to claim 1, wherein the (c3) alkyl (meth) acrylate monomer component comprises a combination of (c4) a copolymer graft-polymerized with a rubber polymer. Composition. 5. The flame-retardant resin composition according to claim 1, further comprising polytetrafluoroethylene.