JPH10279814A - Production of flare-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which is excellent in flame retardance and dripping prevention effect and is suitable for injection molding by crushing a fluororesin, blending a thermoplastic rein with the crushed fluororesin and a flame retardant, and melt kneading the resultant blend. SOLUTION: 100 pts.wt. thermoplastic resin is compounded with 0.01-5 pts.wt. fluororesin and 0. 1-30 pts.wt. flame retardant. The fluororesin is crushed at -5 deg.C or lower in advance and then is blended with the thermoplastic resin at 10 deg.C or lower before melt kneading. Pref., the thermoplastic resin comprises 5-98 wt.% polycarbonate resin and 95-2 wt.% rubber-reinforced resin which comprises a vinyl polymer and a graft polymer obtd. by grafting at least one vinyl compd. onto a rubbery polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition comprising a thermoplastic resin, a flame retardant, and a fluororesin and having high flame retardancy, and a method for producing the same.

[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
es) In order for a resin to be ranked at a high flame retardance level in the UL fire test (UL94) according to regulations, it is important that the test piece does not drip during the UL fire test, preventing fire spread in an actual fire. Therefore, prevention of resin dripping is an important issue.

In response to such a demand, a dripping inhibitor has been added to a thermoplastic resin in order to prevent dripping of the resin during combustion. For example, Japanese Patent Publication No. 59-36657
No. JP-A-60-13844 discloses a resin composition comprising polytetrafluoroethylene,
JP-A-61-89241, JP-A-63-1354
No. 42, JP-A-4-249563, JP-A-6
In JP-A-49311, the molecular weight, shape, and particle size of the polytetrafluoroethylene to be blended are specified, but nothing is described about the shape and form in the composition, and there is no description of the production method.

[0004] In the resin composition described in JP-A-3-190958, a silicone resin is added for the purpose of preventing dripping. However, these are inherently inferior in compatibility with the resin, so that the dispersion is poor. The expected anti-dripping performance cannot be sufficiently achieved. Further, there are problems such as a decrease in mechanical properties, breakage of strands during extrusion processing, and clogging of a screen mesh.

[0005] In recent years, in the OA field, coloring is mainly performed by adding a coloring material, and coating is not often performed. Thus, problems such as flow marks and poor surface appearance have occurred during molding.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a flame-retardant resin composition which has excellent flame retardancy, has an excellent dripping prevention effect, and has an excellent surface appearance, and is particularly suitable for injection molding. And a method for producing the same.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the fluororesin is pulverized and melt-kneaded to form the fluororesin in the resin composition. By controlling to a specific form, dripping prevention performance was greatly improved, and it was found that flame retardancy and surface appearance were excellent, and the present invention was accomplished.

That is, the present invention is as follows. 1) With respect to 100 parts by weight of (A) thermoplastic resin, (B) 0.01 to 5 parts by weight of a fluororesin, (C) 0.1 to 5 parts by weight of a flame retardant
A method for producing a flame-retardant resin composition containing 30 parts by weight, wherein a fluororesin (B) is pulverized at -5 ° C or less,
A method for producing a flame-retardant resin composition, which comprises blending with a thermoplastic resin (A) at a temperature of not more than ° C and melt-kneading.

2) (A) a thermoplastic resin comprising (D) 5 to 98 parts by weight of a polycarbonate resin, and one or more vinyls copolymerizable with a rubbery polymer and the rubbery polymer; Rubber-reinforced resin (E) containing a graft polymer obtained by graft-polymerizing a compound and a vinyl polymer;
2. The method for producing a resin composition according to the above item 1, comprising 2 parts by weight.

3) The method for producing a resin composition as described in 1 or 2 above, wherein (B) the fluororesin is a tetrafluoroethylene (TFE) resin. 4) The method for producing a resin composition according to the above 1, 2 or 3, wherein (C) the flame retardant is a condensed phosphate ester flame retardant. 5) A resin composition produced by the production method according to any one of 1 to 4 above, wherein the tensile fracture surface of the UL94 test piece is observed in an area of 7 μm × 7 μm to show the fibril of the fluororesin. A resin composition characterized in that 70% or more of the total elongation has a thickness of 0.5 micron or less, and a portion where a network structure and / or a branched structure is present in 10 or more places is observed.

6) A molded article comprising the resin composition as described in 5 above. Hereinafter, the present invention will be described in detail. Examples of the thermoplastic resin (A) used in the present invention include engineered plastics such as polystyrene resin, polyolefin resin, polyamide resin, polyoxymethylene resin, polyphenylene ether resin, polycarbonate resin, and polyester resin. And polymethyl methacrylate-based resins. These may be used alone or as a mixture of two or more. Of these, polystyrene-based resins, polyester-based resins, and polycarbonate-based resins are preferred. The polystyrene resin is a rubber-modified styrene resin, a rubber-unmodified styrene resin, or the like.

The above rubber-modified styrenic resin, or
Examples of the vinyl monomer used in the rubber-unmodified styrene resin include aromatic vinyl compounds such as styrene, α-methylstyrene, and paramethylstyrene, and alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, butyl acrylate, and ethyl acrylate. ) Acrylates,
(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 monomers such as N-cyclohexylmaleimide, and glycidyl group-containing monomers such as glycidyl methacrylate are exemplified, but aromatic vinyl compounds, alkyl (meth) acrylates, and vinyl cyanide monomers are preferred. And maleimide monomers, more preferably styrene, acrylonitrile, N-phenylmaleimide, and butyl acrylate.

These vinyl compounds can be used alone or in combination of two or more. Rubber-modified polystyrene-based resin refers to a polymer in which a rubbery polymer is dispersed in a matrix in a matrix composed of a vinyl aromatic polymer, and an aromatic vinyl monomer in the presence of the rubbery polymer, It can be obtained by subjecting a monomer mixture to which a vinyl monomer copolymerizable therewith is added, if necessary, to bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization by a known method.

Examples of such resins include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin, (acrylonitrile-acrylic rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene copolymer). Propylene rubber-styrene copolymer). As the rubbery polymer, any one 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,
Block copolymers such as ethylene-propylene rubber, ethylene-propylene-diene terpolymer rubber, styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, and hydrogenated products thereof can be used. .

The polycarbonate resin (D) 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 in particular, 2,2-
Bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) is preferred. Further, part or all of bisphenol A may be substituted with another dihydric phenol compound. Examples of the dihydric phenol compound other than bisphenol A include hydroquinone, 4,4 dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone,
Compounds such as bis (4-hydroxyphenyl) ketone. A homopolymer of these dihydric phenols, a copolymer of two or more thereof, or a blend thereof may be used.

Next, the rubber reinforced resin (E) used in the present invention
Is described below. The rubber-reinforced resin can be obtained by graft-polymerizing a vinyl compound capable of being graft-polymerized to a rubber-like polymer, and may include a vinyl polymer which is simultaneously polymerized in the polymerization process. Moreover, you may mix | blend and polymerize a vinyl polymer simultaneously or separately.

The rubbery polymer includes polybutadiene, polyisoprene, polychloroprene, butadiene-
Styrene copolymers, conjugated diene rubbers such as butadiene-acrylonitrile copolymers, and acrylic rubbers such as ethylene-propylene rubber, ethyl acrylate, and butyl acrylate are preferred. A styrene copolymer and a butadiene-acrylonitrile copolymer. Also,
These can be used in combination of two or more.

The content of the rubbery polymer in the rubber reinforced resin is 5 to 60% by weight, preferably 10 to 50% by weight. If the amount is less than 5% by weight, sufficient impact resistance may not always be obtained, and if it exceeds 60% by weight, fluidity and gloss during molding may be reduced. The preferred particle size of the rubber-like polymer in the rubber-reinforced resin is not particularly limited because it differs depending on the type of the vinyl polymer serving as the matrix.For example, in the case of an ABS resin, the particle size is from the viewpoint of impact resistance and gloss. It is preferably from 150 to 600 nm, more preferably from 200 to 500 nm, and still more preferably from 25 to 500 nm.
0 to 450 nm.

Examples of the vinyl compound that can be graft-polymerized on the rubbery polymer include aromatic vinyl compounds such as styrene, α-methylstyrene and paramethylstyrene, methyl methacrylate, methyl acrylate, butyl acrylate, and the like.
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 , Maleimide monomers such as N-phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide, and glycidyl group-containing compounds such as glycidyl methacrylate, but preferably aromatic vinyl compounds and alkyl (meth) An acrylate, a vinyl cyanide compound, and a maleimide-based compound are preferable, and styrene, acrylonitrile, N-phenylmaleimide, and butyl acrylate are more preferable.

These vinyl compounds can be used alone or in combination of two or more. The vinyl polymer that can be contained in the rubber-reinforced resin (E) is a polymer or copolymer of the following vinyl compound. As the vinyl compound, 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 compounds such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as maleic anhydride; Maleimide-based compounds such as -phenylmaleimide, N-methylmaleimide, and N-cyclohexylmaleimide; and glycidyl group-containing compounds such as glycidyl methacrylate. Preferred are aromatic vinyl compounds, alkyl (meth) acrylates, and cyanide. Vinyl compounds and maleimide compounds, more preferably styrene, acrylonitrile, N-phenylmaleimide, and butyl acrylate.

These vinyl compounds can be used singly, in combination of two or more, or copolymerized. As a method for producing a rubber-reinforced resin in the present invention,
Although not particularly limited, an emulsion graft polymerization system in which a vinyl compound is graft-polymerized to a rubber-like polymer latex produced by emulsion polymerization, and a two-stage polymerization method in which emulsion graft polymerization is combined with solution polymerization or suspension polymerization, and the like Is exemplified. These can be any of a continuous type, a batch type, and a semi-batch type. In addition, a graft polymer having a high rubber content is prepared in advance by the above method, and then a thermoplastic resin containing a vinyl compound as a main component used at the time of graft polymerization produced by bulk polymerization, emulsion polymerization or suspension polymerization is compounded. A method for reducing the rubber content is described.

In the present invention, an emulsion graft system in which a vinyl compound is continuously added to a rubber-like polymer produced by emulsion polymerization together with an initiator, a molecular weight regulator and the like is preferable. The pH at the time of polymerization is not particularly limited, but is preferably around neutral (pH 7 to 9) from the viewpoint of the graft reaction. In the present invention, the thermoplastic resin (A) is preferably composed of (D) a polycarbonate-based resin and (E) a rubber-reinforced resin.
It is determined according to molding workability, heat resistance and the like, but usually (D) is in the range of 98 to 5 parts by weight, (E) is in the range of 2 to 95 parts by weight, and preferably (D) is in the range of 80 to 20 parts by weight. Department,
(E) is 20 to 80 parts by weight, more preferably (D) is 70 to 30 parts by weight, and (E) is 30 to 70 parts by weight.

The fluororesin (B) used in the present invention is generally a tetrafluoroethylene (TF)
E) Resin, perfluoroalkoxy (PFA) resin, fluorinated ethylene propylene (FEP) resin, etc., and particularly preferably TFE resin. In the resin composition, fibrils having a thickness of 0.5 μm or less are mainly used. In the form of a fibril having a network structure and / or
It is preferably present in a branched form.

The compounding amount of the fluororesin is preferably 0.01 to 5 parts by weight. If the amount is less than 0.01 part, the effect of preventing dripping is not sufficient, and if it exceeds 5 parts by weight, the mechanical strength of the resin is increased. And the processing fluidity decreases. More preferably, 0.
The amount is from 02 to 2 parts by weight, particularly preferably from 0.1 to 1 part by weight. In the present invention, the form of the fluororesin is specifically observed by the following method. That is, U of the resin composition
The presence of the above-mentioned fibrils is measured by molding a test piece for L94 combustion test by injection molding and observing the tensile fracture surface of the test piece by a scanning electron microscope (SEM). In the present invention, other conditions are not particularly limited,
The measurement was performed under the following conditions.

[Injection molding] Molding machine: M-JEC10 (manufactured by Modern Machinery) Molding temperature: 240 ° C. Mold temperature: 50 ° C. Injection speed: 500 (set value) Test piece: 1/2 × 5 × 1/16 inch [Preparation of Sample for SEM Observation] Using a tensile tester (Autograph 5000D, manufactured by Shimadzu Corporation) at a speed of 5
Pull until breaking at mm / min.

[SEM observation] Pretreatment: gold evaporation is performed on the sample. SEM: JSM-5300 (manufactured by JEOL Ltd.) Acceleration voltage: 15 kV An example of a fluorine-based resin existing in a network structure and / or a branched structure according to the present invention is illustrated and described below with reference to FIGS. . FIG. 1 is a schematic diagram showing the form of the fluororesin, and FIGS. 2 to 5 are SEM photographs.

As for the form of the fluororesin, it is preferable that a portion satisfying the following condition is observed by observing a range of 7 μm × 7 μm of the tensile fracture surface of the test piece for UL94 test. The fluororesin is a portion indicated by a solid black line in FIG. 1 and a portion that looks white in FIGS.

It is preferable that the fibrils of the fluororesin mainly have a thickness of 0.5 μm or less.
The presence of fibrils with a thickness of 0.5 micron or more is possible, for example, as shown in FIG.
70 of the total fibril extension observed in the micron range
%, Preferably 90% or more exists at 0.5 micron or less.

In the present invention, the network structure is
A portion where two or more fibrils are observed to be overlapped or a system in which fibrils are interconnected as shown in FIG. Further, the branched structure refers to a portion where two or more fibrils are separated from one point shown in a portion b of FIG. Both the network structure and the branch structure have a three-dimensional spread.

Further, in the present invention, at least 10 portions of these network structures and / or branch structures are observed in a range of 7 μm × 7 μm. That is, the network structure and branch structure observed by SEM do not necessarily indicate the network structure and branch structure in the resin composition, but reflect the dense presence of fibrils in the resin composition, The presence of the network structure and / or the branched structure is regarded as the presence of the network structure and / or the branched structure in the resin composition.

It is presumed that due to the presence of such a dense fibril form of the fluororesin, fibril shrinkage during combustion occurs three-dimensionally, and effective drip prevention can be achieved. The flame retardant (C) in the present invention is a so-called general flame retardant, and in addition to phosphorus compounds and halogen compounds, nitrogen-containing organic compounds such as melamine, inorganic compounds such as magnesium hydroxide and aluminum hydroxide, Metal oxides such as zinc oxide and tin oxide; and inorganic phosphorus such as red phosphorus, phosphine, hypophosphorous acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, and phosphoric anhydride. Compounds, fibers such as carbon fiber and glass fiber, expanded graphite, silica, silica-based glass melts and the like are used, preferably phosphorus-based compounds or halogen-based organic compounds, and a combination of halogen-based organic compounds and antimony oxide It is.

The halogen-based organic compounds include general halogen-based flame retardants and halogen-containing phosphoric esters in general. For example, examples of the halogen-based organic compound include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, tetrabromophthalimide, and hexabromodiphenyloxide. Bromobutene, hexabromocyclododecane and the like are preferred, and a halogen-based organic compound having the following structure (1) is preferable, and a halogen-based organic compound of the following (2) is particularly preferable.

[0033]

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[0034]

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On the other hand, examples of the halogen-containing phosphoric acid ester include tris-chloroethyl phosphate, tris-dichloropropyl phosphate, tris-β-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, and tris (tribromophenyl) phosphate. There are tribromoneopentyl phosphate) and condensed phosphates thereof, and preferably tris (tribromoneopentyl phosphate), tris (tribromophenyl) phosphate, and tris (dibromophenyl) phosphate. These halogen-based organic compounds can be used alone or in combination of two or more.

Examples of the phosphoric ester flame retardants include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, and tricixyl phosphate. There are phosphoric acid esters such as nyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, and compounds obtained by modifying these with various substituents.

As the flame retardant used in the present invention, a condensed phosphate ester flame retardant is preferred. The condensed phosphate ester flame retardant has a general formula:

[0038]

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(Where n is a positive number from 1 to 10;
1 to Ar4 are each independently a phenyl group, a tolyl group or a xylyl group. When n is 2 or more, a plurality of Ar4 may be the same or different. ), Preferably

[0040]

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(Wherein, 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, and R = A4. The phosphoric acid ester compound represented by the formula (1) is particularly good in flame retardancy and heat resistance. These can be used alone or in combination of two or more.

The amount of the flame retardant is determined according to the required level of flame retardancy, but it is necessary to be 0.1 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin.
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 will be reduced.
It is preferably in the range of 1 to 25 parts by weight, and particularly preferably 3 to 22 parts by weight.

When a halogen compound is used as a flame retardant, a flame retardant auxiliary can be used to enhance the flame retardant effect. Preferably, the flame retardant aid is a compound containing an element belonging to VB in the periodic table of elements, specifically, a nitrogen-containing compound, a phosphorus-containing compound, antimony oxide, bismuth oxide, and the like. Metal oxides such as zinc and tin oxide are also effective. Of these, antimony oxide is particularly preferable, and specific examples thereof include antimony trioxide and antimony pentoxide. These flame-retardant aids may be those which have been subjected to a surface treatment for the purpose of improving dispersion in the resin and / or improving the thermal stability of the resin.

The amount of the flame retardant aid is preferably 0.5 to 20 parts by weight. If the amount is less than 0.5 part, the effect of the flame retardant aid is not sufficient, and if it exceeds 20 parts by weight, the mechanical strength and processing fluidity of the resin tend to decrease. It is more preferably 1 to 15 parts by weight, particularly preferably 1 to 10 parts by weight. Next, the production method of the present invention in which the fluororesin has the above-described form will be described in detail.

For example, when fine powder is used as the fluororesin, it is necessary to pulverize it at a temperature not higher than 0 ° C. Examples of the type of the crusher include a ball mill, an edge runner, a roll crusher, a roller mill, a disk crusher, a stone mill, a mortar, and the like, and preferably, a hammer crusher, a mill for rotating fins at high speed, and the like.

It is particularly important to control the temperature at the time of pulverization. The fluorine resin is cooled to 0 ° C. or lower, preferably −5 ° C. or lower, more preferably −10 ° C. or lower before being charged into the pulverizer. It is preferable to keep it. Furthermore, at the time of grinding,
Since heat is generated, it is necessary to remove the generated heat, and the temperature of the fluororesin during the pulverization is maintained at -5 ° C or lower, preferably -10 ° C or lower, more preferably -20 ° C or lower. preferable. For this purpose, for example, there is a method of pulverizing a fluororesin together with pulverized dry ice. If the temperature exceeds -5 ° C, the fluororesin tends to agglomerate, and the ability to prevent dripping is inferior.

Next, the raw material resin or the like, that is, a blend with a thermoplastic resin, a flame retardant, or the like is blended.
It is necessary to cool and blend below. 10 ℃
When the ratio exceeds, the fluororesin tends to aggregate, and the ability to prevent dripping is inferior. Melt kneading can be performed by a known method, and is not particularly limited. For example, there is a method in which each component is uniformly mixed with a Henschel mixer, a super mixer, a turn bull mixer, a ribbon blender or the like, and then melt-kneaded with a single-screw extruder, a twin-screw extruder, a Banbury mixer or the like. In that case, as long as the gist of the present invention is not hindered,
It is optional to add known additives such as antioxidants, ultraviolet absorbers, lubricants, release agents, antistatic agents, and coloring agents.

The method for molding a molded article comprising the flame-retardant resin composition thus obtained includes extrusion molding, compression molding, injection molding, gas assist molding and the like, and is not particularly limited. Examples of the molded product include an OA equipment housing, an OA equipment chassis, a wheel cap, a spoiler, and an instrument panel of an automobile.

[0049]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples and comparative examples of the present invention will be described below. In addition, the measuring method is as follows. (1) Morphological Observation Method The tensile fracture surface of the UL94 test piece was observed by the method described above. As a result, a resin composition in which the above-mentioned network structure and / or the form of the fluorine-based resin existing in a branched state was observed was indicated by a circle, and a resin composition in which the form was not observed was indicated by a cross.

(2) Glossiness The resin was injection-molded at a temperature suitable for each resin composition.
Form a flat plate of 0cm × 10cm × 2mm and use ASTM-
Based on D-523-62T, a gloss meter (Glossme
ter), the surface gloss was determined by setting the incident angle and the reflection angle to 60 degrees. (3) Flow mark 1 Injection molded at a temperature suitable for each resin composition
A flat plate of 0 cm × 10 cm × 2 mm was formed, and the surface was visually inspected for flow marks or silver. ：: No flow mark or silver was generated. X: Flow mark or silver was generated. (4) Flame retardancy Measured by a test based on the UL94 standard vertical combustion test (thickness 1/16 inch).

Next, the compounding agents (hereinafter, also referred to as raw materials) used in the examples will be described below. The number of parts is by weight. (Polycarbonate resin A-1) weight average molecular weight 22,
500 bisphenol A-based polycarbonate resin. The weight average molecular weight was measured by gel permeation chromatography (GPC). Column: polystyrene gel, solvent: THF.

(Polyphenylene ether resin A-2) 75 parts by weight of poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter abbreviated as PPE) resin and a general polystyrene resin having a weight average molecular weight of 210,000 25
Modified PPE resin obtained by melt-kneading parts by weight. The PPE is prepared by oxidative coupling polymerization of 2,6-xylenol in the presence of dibutylamine according to the method described in U.S. Pat. No. 4,788,277 (Japanese Patent Application No. 62-77570). The PP
E is ηsp / c = 0.42 and the viscosity is 280 ° C.
At a shear rate of 140 sec ^-1 at 49000 po
is.

(Rubber reinforced resin A-3) butadiene component 1
An acrylonitrile-butadiene-styrene resin (ABS resin) comprising 0% by weight, 66% by weight of a styrene component, and 24% by weight of an acrylonitrile component. (Rubber reinforced resin A-4) A rubber reinforced resin comprising 20% by weight of a butadiene component, 18% by weight of an acrylonitrile component, 50% by weight of a styrene component, and 12% by weight of an N-phenylmaleimide component.

(Rubber reinforced resin A-5) butadiene component 1
High impact polystyrene resin (HIPS resin) comprising 0% by weight and 90% by weight of a styrene component. (Flame retardant FR-1) A compound represented by the above formula (2), wherein n = 0 or a natural number, and R and R ′ are each a group represented by the formula (4), and have a softening temperature of 105 ° C. Is a flame retardant.

(Flame Retardant FR-2) Triphenyl Phosphate (Flame Retardant FR-3) A condensed phosphate ester-based flame retardant containing a mixture of the above formulas (7) and (8) as a main component. Synthesized.

114 g (0.5 mol) of bisphenol A, 192 g (1.25 mol) of phosphorus oxychloride, and 1.4 g (0.015 mol) of anhydrous magnesium chloride
Was charged into a 500 ml four-necked flask equipped with a stirrer and a reflux tube, and reacted at 70 to 140 ° C. for 4 hours under a nitrogen stream. After completion of the reaction, the flask was evacuated to a pressure of 200 mmHg or less by a vacuum pump while maintaining the reaction temperature, and unreacted phosphorus oxychloride was collected by a trap.

Then, the flask was cooled to room temperature, and
122 g (1.0 mol) of xylenol and 2.0 g (0.015 mol) of anhydrous aluminum chloride were added, and 100
The mixture was heated to １５０150 ° C. and reacted for 4 hours. Then, the flask was cooled to room temperature and phenol 94 g (1.0 mol) was obtained.
Was added, and heated to 100 to 150 ° C. and maintained for 4 hours to complete the reaction. The pressure was reduced to 1 mmHg at the same temperature, and unreacted phenols were distilled off. Hydrogen chloride gas generated during the reaction is collected with an aqueous sodium hydroxide solution,
The progress of the reaction was monitored by measuring the amount generated by neutralization titration. After the generated crude phosphate was washed with distilled water, the solid content was removed with a filter paper (# 131 manufactured by Advantech). Vacuum drying gave a pale yellow, clear purified product.

As a result of HPLC measurement (LC-10A manufactured by Shimadzu, column: Tosoh TSKgel ODS-80T, solvent: methanol / water 90/10), the total purity of the components of the formulas (7) and (8) was 75% by weight. there were. (Fluorine-based resin TFE-1) DAIFLON F-201L (manufactured by Daikin Industries, Ltd.) (Fluorine-based resin TFE-2) Manufactured by Mitsui Dupont Fluorochemicals, Teflon 62-J

[0059]

Examples 1 to 5 and Comparative Examples 7 and 8 In accordance with the compositions shown in Tables 1 and 2 (units are parts by weight), the following procedures were carried out. Except for the fluororesin and the flame retardant, each raw material was cooled (3 ° C.) and pulverized together with dry ice (sample mill, SK-M10
Molded fluoropolymer (TFE-1, T)
FE-2) was blended and kneaded with a twin-screw extruder (ZSK-25, manufactured by W & P) having a cylinder temperature set at 250 ° C., and was pressed into the resin in which the flame retardant was melted by a pump from the middle of the extruder. The resulting pellets were evaluated. The results are shown in Tables 1 and 2.

[0060]

Examples 6 to 8 In accordance with the composition (unit is part by weight) in Table 1,
This was performed as follows. After cooling the raw materials (3 ° C.) except the fluororesin, the fluororesins (TFE-1 and TFE-2) pulverized (sample mill, SK-M10 type, manufactured by Kyoritsu Riko Co., Ltd.) with dry ice were used. Blend, twin screw extruder (ZS) with cylinder temperature set at 250 ° C
(K-25, manufactured by W & P) and granulated, and the obtained pellets were evaluated. Table 1 shows the results.

[0061]

Comparative Examples 1, 2, 6, 9 Compositions in Table 2 (units are parts by weight)
And performed as follows. Except for the flame retardant, each material was blended (room temperature, 25 ° C) and the cylinder temperature was 2
Twin screw extruder set at 50 ° C (ZSK-25, W & P
The product was kneaded by a pressurizer, and the flame retardant was injected into the melted resin by a pump from the middle of the extruder, granulated, and the obtained pellets were evaluated. Table 2 shows the results.

[0062]

Comparative Examples 3 to 5 According to the composition (unit is part by weight) in Table 2,
This was performed as follows. Blend each material (room temperature, 2
5 ° C.), and kneaded and granulated with a twin-screw extruder (ZSK-25, manufactured by W & P) having a cylinder temperature set at 250 ° C., and the obtained pellets were evaluated. Table 2 shows the results.

[0063]

[Table 1]

[0064]

[Table 2]

From the above Examples and Comparative Examples, it was found that all of the resin compositions of Examples were excellent in flame retardancy and surface appearance.

[0066]

The flame-retardant resin composition of the present invention has a high fluorine-containing resin content due to the presence of a network structure and / or a branched structure in the resin composition. It is possible to obtain a molded article having excellent flame retardancy, excellent drip prevention effect, and excellent surface appearance.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a fibril form of a fluororesin in a fracture surface of a molded article of a flame-retardant resin composition of the present invention. In FIG. 1, the portion indicated by the solid black line is a fluororesin.

FIG. 2 is a scanning electron microscope photograph of a fibril morphology of a fluorine-based resin on a fractured surface of a resin composition molded article of Example 2.

FIG. 3 is a scanning electron micrograph showing a fibril morphology of a fluororesin in a fractured surface of a resin composition molded article of Example 4.

FIG. 4 is a scanning electron micrograph showing the fibril morphology of the fluororesin in the fracture surface of the resin composition molded product of Example 5.

FIG. 5 is a scanning electron micrograph of a fibril morphology of a fluororesin on a fracture surface of a resin composition molded product of Comparative Example 6; In FIGS. 2 to 5, the portion observed white is the fluorine-based resin.

[Explanation of symbols]

 a Network structure b Branch structure

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[Submission date] April 9, 1997

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Claims (6)

[Claims] 1. A flame-retardant resin in which (A) 0.01 to 5 parts by weight of a fluorinated resin and (C) 0.1 to 30 parts by weight of a flame retardant are blended with respect to 100 parts by weight of a thermoplastic resin. A flame-retardant resin, which is a method for producing a composition, wherein a fluorine-based resin (B) is pulverized at -5 ° C or lower, blended with a thermoplastic resin (A) at 10 ° C or lower, and melt-kneaded. A method for producing the composition. 2. A thermoplastic resin comprising: (D) 5 to 98 parts by weight of a polycarbonate resin; and one or more vinyls copolymerizable with the rubbery polymer and the rubbery polymer. Rubber reinforced resin (E) 95-2 containing a graft polymer obtained by graft polymerization of a compound and a vinyl polymer
The method for producing a resin composition according to claim 1, comprising parts by weight. 3. The method for producing a resin composition according to claim 1, wherein (B) the fluororesin is a tetrafluoroethylene (TFE) resin. 4. The method for producing a resin composition according to claim 1, wherein (C) the flame retardant is a condensed phosphate ester flame retardant. 5. A resin composition produced by the production method according to claim 1, wherein the tensile fracture surface of the UL94 test specimen is fluorine-based when observed in a range of 7 μm × 7 μm. A resin characterized in that 70% or more of the total elongation of fibrils of the resin has a thickness of 0.5 micron or less, and a portion where a total of 10 or more network structures and / or branch structures are present is observed. Composition. 6. A molded article comprising the resin composition according to claim 5.