JPH0959505A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition which is useful for computers because the antisagging effect is effectively developed to show excellent balance between the flame retardance and the mechanical properties with no damage to other properties by adding a flame retardant to a polycarbonate resin at a specific ratio. SOLUTION: This flame-retardant resin composition comprises (A) 70-99.9 pts.wt. of a polycarbonate resin with a weight-average molecular weight of 7,000-35,000, (B) 30-0.1 pts.wt. of a polycarbonate resin with a weight-average molecular weight of 40,000-300,000, totaling to 100 pts.wt., (C) 0.1-30 pts.wt. of a flame retardant for example of a phosphorus compound of formula I (R1 -R4 are each an aryl, an alkaryl; X is an arylene; (i), (k), (l), (m) are each 0, 1; (n) is a natural number). In a preferred embodiment, 0.1-30 pts.wt. of the component C is formulated to 100 pts.wt. of 1-99 pts.wt. of components A and B and (D) 1-99 pts.wt. of a rubber-toughened resin comprising a graft polymer prepared by grafting a vinyl compound onto a rubber polymer and a vinyl copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent flame retardancy. Furthermore, it relates to a resin composition having excellent injection moldability.

[0002]

2. Description of the Related Art Along with the tightening of flame retardant regulations, resin flame retardant technology has become an important technology in various fields, especially OA fields such as computers, word processors and copiers, televisions, and the like.
It is becoming one of the indispensable characteristics in the field of general home appliances such as game machines. Underwriter Laboratories
s) In order for a resin to be ranked at a high flame retardance level in the UL Fire Test by Regulation (UL94), the test piece must
It is important not to drip in the process of the L burning test, and to prevent fire spread in an actual fire, prevention of dripping of the resin is an important issue.

In response to such a demand, a kind of thermoplastic resin represented by a polycarbonate resin is added with an anti-dripping agent for the purpose of preventing the resin from dripping during combustion. For example, the resin compositions described in JP-B-59-36657 and JP-A-60-13844 are polytetrafluoroethylene, JP-A-3-1909.
In the resin composition described in JP-A-58, a silicon resin is added for the purpose of preventing dripping, but these are originally inferior in compatibility with the resin, and mechanical properties are lowered, or strand breakage occurs during extrusion processing. In addition to having drawbacks such as causing the screen mesh and causing clogging of the screen mesh, there is a problem that it is economically disadvantageous. Also,
Japanese Patent Application Laid-Open No. 4-342760 describes a resin composition having excellent drawdown properties for blow molding, but does not describe flame retardancy.

[0004]

The problem to be solved by the present invention is that it has an excellent effect of preventing dripping and is excellent in the balance of flame retardancy and mechanical properties, particularly flame retardancy for injection molding. It is to provide a resin.

[0005]

That is, the present invention is as follows.
(A) 70 to 99.9 parts by weight of a polycarbonate resin having a weight average molecular weight of 7,000 to 35,000, (B) 30 to 0.1 parts by weight of a polycarbonate resin having a weight average molecular weight of 40,000 to 300,000, and 100 in total of (A) and (B). The flame-retardant resin composition comprises 0.1 to 30 parts by weight of (C) a flame retardant with respect to parts by weight.

Further, the total amount of the polycarbonate resins (A) and (B) is 1 to 99 parts by weight, and (D) a rubber-reinforced resin comprising a vinyl copolymer grafted with a vinyl compound and a vinyl copolymer. 99-1 parts by weight, (A)
And (B) and (D) for a total of 100 parts by weight, (E)
The flame retardant is preferably 0.1 to 30 parts by weight.
Hereinafter, the present invention will be described in detail.

The polycarbonate resin (A) used in the present invention is produced by reacting a dihydric phenol with phosgene or a carbonic acid diester. As the dihydric phenol, bisphenols are preferable, and 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) is particularly preferable. Further, part or all of bisphenol A may be substituted with another dihydric phenol compound. The dihydric phenol compound other than bisphenol A is, for example, a compound such as hydroquinone, 4,4 dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, or bis (4-hydroxyphenyl) ketone. is there. A homopolymer of these dihydric phenols, or
It may be a copolymer of two or more kinds or a mixture thereof.

The molecular weight of the polycarbonate resin (A) is in the range of 7,000 to 35,000. If it is less than 7,000, the mechanical strength is insufficient and the heat distortion temperature becomes low. On the other hand, if it is larger than 35,000, the melt fluidity is lowered. The high molecular weight polycarbonate resin (B) in the present invention is produced by the reaction of a dihydric phenol with phosgene or a carbonic acid diester. As the dihydric phenol, bisphenols are preferable, and 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) is particularly preferable. Further, part or all of bisphenol A may be substituted with another dihydric phenol compound. The dihydric phenol compound other than bisphenol A is, for example, a compound such as hydroquinone, 4,4 dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, or bis (4-hydroxyphenyl) ketone. is there. A homopolymer of these dihydric phenols, or
It may be a copolymer of two or more kinds or a mixture thereof. Further, the polycarbonate resin (A) may have a different structure, but the same structure is preferable.

The high molecular weight polycarbonate resin (B) has a molecular weight in the range of 40,000 to 300,000, preferably 45,000 to 120,000. When it is less than 40,000, the effect of improving dripping prevention is small. Also, 30,000
If it exceeds 0, there is a problem in that it is not uniformly dispersed during melt-kneading. The composition ratio of the polycarbonate resin (A) and the high molecular weight polycarbonate resin (B) is 70 to 99.9 parts by weight of the polycarbonate resin (A) and 30 to 0.1 parts by weight of the high molecular weight polycarbonate resin (B). Preferably, the polycarbonate resin (B) is 0.3 to
10 parts by weight, 90 to 9 of polycarbonate resin (A)
9.7 parts by weight, more preferably 99.7 to 95 parts by weight of the polycarbonate resin (A) and 0.3 to 5 parts by weight of the high molecular weight polycarbonate resin (B). When the blending amount of the high molecular weight polycarbonate resin (B) is less than 0.1 part by weight, the dripping prevention effect is hardly exhibited and
If it is larger than the area, it becomes difficult to process and the effect of preventing dripping decreases.

Components (C) and (E) used in the present invention
The flame retardant is a so-called general flame retardant, in addition to phosphorus-based compounds and halogen-based organic compounds, nitrogen-containing organic compounds such as melamine, magnesium hydroxide, inorganic compounds such as aluminum hydroxide, antimony oxide, bismuth oxide, Expanded graphite, low melting point glass and the like are used, but phosphorus compounds, halogen organic compounds, and halogen organic compounds and antimony oxide are preferably used.

Examples of phosphorus compounds include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate,
Phosphoric acid esters such as tricresyl phosphate, trixylenyl phosphate, dimethylethyl phosphate, methyldibutyl phosphate, ethyldipropylphosphate, hydroxyphenyldiphenylphosphate and compounds modified with these various substituents, or red phosphorus, phosphine, Phosphorous acid, phosphorous acid, metaphosphoric acid,
Inorganic phosphorus compounds such as pyrophosphoric acid and anhydrous phosphoric acid.

Preferred are compounds represented by the general formula (1).

[0013]

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More preferred are the phosphoric acid ester compounds represented by the general formulas (2) to (5).

[0015]

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(In the formula, Ar1 to Ar3 are the same or different, and each represents a phenyl group, a tolyl group, or 2,6
-A xylyl group other than a xylyl group. In the formula, R is a group selected from the following formulas (A1) to (A4). )

[0017]

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This phosphoric acid ester compound has a particularly good flame retarding effect. These can be used alone or in combination of two or more. Examples of the halogen-based organic compound include, for example, hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, octabromodiphenyl oxide,
There are tetrabromobisphenol A, tetrabromophthalimide, hexabromobutene, trichlorotetrabromophenyl-triphosphate, and hexabromocyclododecane, but a halogen-based organic compound having a structure of the following general formula (6) is preferable.

[0019]

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Further, metal oxides such as iron oxide, zinc oxide and tin oxide, carbon fiber, glass fiber,
Fibers such as may be used together as a flame retardant aid. Phosphorus,
The content of the halogen-based organic compound is determined according to the required level of flame retardancy, but the total amount of the resin composition is 10
It is 0.1 to 30 parts by weight with respect to 0 parts by weight. It is preferably 1-28 parts by weight, more preferably 5-25 parts by weight. If the amount is less than 0.1 part by weight, the required flame retardant effect is not exhibited. If it exceeds 30 parts by weight, the mechanical strength of the resin is lowered.

The rubber-reinforced resin (D) in the present invention refers to all graft copolymers obtained by graft-polymerizing a vinyl compound in the presence of a rubbery polymer. As the vinyl compound used in the present invention, styrene, α-methylstyrene, aromatic vinyl compounds such as paramethylstyrene, methyl methacrylate, methyl acrylate, butyl acrylate,
Alkyl (meth) acrylates such as ethyl acrylate, (meth) acrylic acids such as acrylic acid and methacrylic acid, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, α, β-unsaturated carboxylic acids such as maleic anhydride , N-phenylmaleimide, N-methylmaleimide, maleimide-based monomers such as N-cyclohexylmaleimide, and glycidyl group-containing monomers such as glycidylmethacrylate, but preferably aromatic vinyl compounds and alkyl (meth). Acrylates, vinyl cyanide monomers, and maleimide-based monomers are more preferable, and styrene, acrylonitrile, N-phenylmaleimide, and butyl acrylate are more preferable.

These vinyl compounds may be used alone or in combination of two or more. Preferably,
It is a combination of an aromatic vinyl compound and a non-aromatic vinyl compound. In this case, the aromatic vinyl compound and the non-aromatic vinyl compound can be copolymerized at any ratio, but preferably in the range of 5 to 80% by weight. Any rubbery polymer having a glass transition temperature of 0 ° C. or lower can be used. Specifically, polybutadiene, styrene-
Diene rubber such as butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, polyisoprene, polychloroprene, ethylene-propylene rubber, ethylene-propylene-diene terpolymer rubber, styrene Block copolymers such as a butadiene block copolymer rubber and a styrene-isoprene block copolymer rubber, and hydrogenated products thereof can be used.

Of these polymers, polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, polybutyl acrylate and the like are preferable. The proportion of the rubbery polymer in the graft copolymer is used in the range of 30 to 95% by weight,
From the viewpoint of the balance between impact resistance and working fluidity, preferably 5
It is in the range of 0 to 90% by weight.

In the graft copolymer, the ratio of the grafted component to the rubbery polymer and the non-grafted component is specifically determined by dissolving the polymer produced by the polymerization in acetone,
It can be measured by separating and removing the insoluble matter with a centrifuge. The component that dissolves in acetone is the component that did not undergo graft reaction in the copolymerized polymer (non-graft polymer), and the value obtained by subtracting the amount of rubber polymer from the acetone insoluble content is defined as the value of the graft component. To be done.

It is also possible to use it together with a conventional anti-dripping agent. Examples of conventional anti-dripping agents include perfluoroalkane polymers such as polytetrafluoroethylene, silicone rubber, glass fibers and carbon fibers. For the purpose of modifying the resin, the resin composition of the present invention contains, if necessary, conventional additives, that is, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a colorant, titanium oxide, and a surface. A modifier, a dispersant, a plasticizer, a stabilizer and the like can be added.

The method for producing the resin composition in the present invention is not particularly limited, and the resin composition can be produced by an ordinary method, for example, melt blending by extrusion kneading. The resin composition of the present invention, by blending a high-molecular weight polycarbonate resin, effectively exhibits a dripping prevention effect at the time of combustion, and is compatible with the polycarbonate resins, sacrificing other properties. The resin composition has a particularly excellent balance of flame retardancy and mechanical properties, and is particularly excellent in injection moldability.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The measurement methods used and the formulations used are described below. The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC). A column was TSK-GEL (manufactured by Toyo Soda Co., Ltd.), a solvent was THF, and a standard substance was TAFRON A2500 (manufactured by Idemitsu Kosan Co., Ltd.).

The flame retardancy is measured based on the UL94 standard vertical combustion test (thickness: 1/12 inch). The Izod impact value is a measurement based on ASTM D256 and the specimen thickness is 1/8 inch and notched. (Unit is kgcm / cm) (Polycarbonate resin PC-1) Weight average molecular weight 2
4,500 polycarbonate resin (polycarbonate resin PC-2) weight average molecular weight 52
600 polycarbonate resin (styrene-based rubber reinforced resin D-1) butadiene component 28
ABS resin (acrylonitrile-containing 51% by weight of styrene component and 21% by weight of acrylonitrile component).
Butadiene-styrene resin). (Styrene-based rubber reinforced resin D-2) An AAS resin (acrylonitrile-butyl acrylate-styrene resin) comprising 20% by weight of a butyl acrylate rubber component, 56% by weight of a styrene component and 24% by weight of an acrylonitrile component. (Flame retardant FR-1) triphenyl phosphate. (Flame Retardant FR-2) CR-741C made by Daihachi Chemical Co., Ltd. (Flame Retardant FR-3) A phosphate ester flame retardant containing the general formula (2) as a main component was synthesized by the following method.

114 g (0.5 mol) of bisphenol A, 154 g (1.0 mol) of phosphorus oxychloride, and 1.4 g (0.015 mol) of anhydrous magnesium chloride were charged into a 500 ml four-necked flask equipped with a stirrer / reflux tube. ,
It was made to react at 70-140 degreeC under nitrogen stream for 4 hours. After completion of the reaction, while maintaining the reaction temperature, the pressure of the flask was reduced to 200 mmHg or less by a vacuum pump, and unreacted phosphorus oxychloride was collected by a trap. Then, the flask was cooled to room temperature, 61 g (0.5 mol) of 2,6 xylenol and 2.0 g (0.015 mol) of anhydrous aluminum chloride were added, and the mixture was heated to 100 to 150 ° C. and reacted for 4 hours. Then the flask was cooled to room temperature and 141 g of phenol
(1.5 mol) and heated to 100-150 ° C. for 4
Hold for time to complete reaction. 1mm at the same temperature
The pressure was reduced to Hg, and unreacted phenols were distilled off. Hydrogen chloride gas generated during the reaction was collected with an aqueous sodium hydroxide solution, and the amount of the generated hydrogen chloride was measured by neutralization titration to monitor the progress of the reaction. After washing the generated crude phosphate ester with distilled water, filter paper (Advantech # 131)
To remove solids. Vacuum drying gave a pale yellow, clear purified product. (Flame Retardant FR-4) In the general formula (6), n = 0 or a natural number, X = bromine, k and l = 2, R and R ′ are the groups described in the general formula (8), and m = 3. Flame retardant represented. (Drip-preventing agent 1) -PTFE (polytetrafluoroethylene) An average particle size (measured according to ASTM-D1457) of 500 µm and a melting point (measured according to JIS-K6891) of 327 ° C. (Drip prevention agent 2) -Acrylic-silicon composite rubber 100 parts of polyorganosiloxane latex, 37.5 parts of n-butyl acrylate, allyl methacrylate 2.
Graft copolymer consisting of 5 parts and 30 parts of methyl methacrylate (one graft-polymerized by the method described in the example of JP-A-64-79257 and the reference example 1 using methyl methacrylate instead of acrylonitrile and styrene) ).

[0030]

Examples 1 to 9 and Comparative Examples 1 to 4 A twin-screw extruder (ZSK-25, manufactured by W & P) blended with the composition shown in Table 1 (unit is parts by weight) and the cylinder temperature was set to 280 ° C. After kneading and granulating with, injection molding machine (cylinder temperature 280
C., mold temperature 75.degree. C., FAS-100B, manufactured by FANUC Co., Ltd.) to obtain test pieces for physical property measurement and combustion test. The results are shown in Table 1.

[0031]

[Table 1]

[0032]

Examples 10 to 18 and Comparative Examples 5 to 9 Blends were made with the compositions shown in Table 2 (unit is parts by weight), and the cylinder temperature was 28.
After kneading and granulating with a twin-screw extruder (ZSK-25, manufactured by W & P) set to 0 ° C., an injection molding machine (cylinder temperature 2)
40 ° C., mold temperature 70 ° C., FAS-100B, manufactured by Fanuc) were used to obtain test pieces for measuring physical properties and for burning test. The results are shown in Table 2.

[0033]

[Table 2]

[0034]

EFFECT OF THE INVENTION The resin composition of the present invention has a particularly excellent balance of flame retardancy and mechanical properties without sacrificing other properties, effectively exhibiting the function of preventing dripping during combustion. In particular, the resin composition has excellent injection moldability.

Claims (3)

[Claims] 1. A weight average molecular weight of 7,000 to 350
00 polycarbonate resin 70 to 99.9 parts by weight,
(B) 30 to 0.1 parts by weight of a polycarbonate resin having a weight average molecular weight of 40,000 to 300,000, (A) and (B)
Flame retardant (C) 0.1 to 100 parts by weight in total.
A flame-retardant resin composition comprising 30 parts by weight. 2. Polycarbonate resins (A) and (B)
1 to 99 parts by weight, (D) 99 to 1 parts by weight of a rubber-reinforced resin comprising a vinyl copolymer grafted with a vinyl compound and a vinyl copolymer, (A) and (B). The flame-retardant resin composition according to claim 1, which comprises 0.1 to 30 parts by weight of the flame retardant (E) with respect to 100 parts by weight of the total of (D). 3. The flame-retardant resin composition according to claim 1, which is molded by injection molding.