WO1997004028A1 - Composition ignifuge a base de resines - Google Patents

Composition ignifuge a base de resines Download PDF

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Publication number
WO1997004028A1
WO1997004028A1 PCT/JP1996/001943 JP9601943W WO9704028A1 WO 1997004028 A1 WO1997004028 A1 WO 1997004028A1 JP 9601943 W JP9601943 W JP 9601943W WO 9704028 A1 WO9704028 A1 WO 9704028A1
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WIPO (PCT)
Prior art keywords
component
weight
parts
compound
flame
Prior art date
Application number
PCT/JP1996/001943
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English (en)
Japanese (ja)
Inventor
Masanao Kawabe
Kiichi Kometani
Takashi Matsuda
Original Assignee
Nippon Steel Chemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from JP17917495A external-priority patent/JPH0931293A/ja
Priority claimed from JP28884695A external-priority patent/JPH09132693A/ja
Application filed by Nippon Steel Chemical Co., Ltd. filed Critical Nippon Steel Chemical Co., Ltd.
Publication of WO1997004028A1 publication Critical patent/WO1997004028A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the present invention relates to a flame-retardant resin composition having excellent mechanical properties provided with excellent flame retardancy without using a hachigen compound.
  • Styrene resins are used in a wide variety of fields, including home appliances and office automation equipment, because of their excellent moldability, dimensional stability, impact resistance, rigidity, and electrical insulation.
  • flame retardant resins are widely used.
  • Various methods have been devised for imparting flame retardancy to flammable resins such as styrene resins, but most commonly halogen-based resins such as bromine compounds having a high flame retardant effect are used.
  • a method is used in which a flame retardant and, if necessary, antimony oxide are added to the resin.
  • a bromine-based or chlorine-based halogen-based flame retardant was used, a large amount of harmful gas was generated due to decomposition of the halogen compound at the time of flame retardation, which caused environmental problems.
  • a method of flame retardation without using a halogen-based flame retardant is being studied.
  • a combination of a phosphorus-containing flame retardant and a nitrogen-containing compound with respect to a resin component is disclosed in Japanese Patent Application Laid-Open No. H4-25253, a) a vinyl aromatic resin, and b) a red phosphorus.
  • a flame-retardant resin composition comprising an organic nitrogen compound and a phenolic or fuanol resin.
  • the organic nitrogen compound used in the publication refers to an organic nitrogen compound such as guanidine, guanamine, azide, azine, diazine, triazine, and the like, and representative examples include melamine, methyl daltalog anamin, aziboguanamine, Succinoguanamine is mentioned.
  • Japanese Unexamined Patent Publication No. Hei 5-333419 discloses a) a thermoplastic resin, b) an organic phosphorus compound and a phosphorus-containing flame retardant that is Z or red phosphorus, and c) a compound containing a triazine skeleton. And c) reducing the weight of the triazine skeleton-containing compound by 10% by weight in a heating test in air (temperature rise rate of 10 ° C.Z min.) Which is an index of the thermal decomposition temperature of the compound. And a low-volatile flame-retardant heat-resistant impact-resistant resin composition characterized by having a triazine skeleton at a temperature of 300 ° C. or higher. A resin composition in which the particle size range of the contained compound is specified is disclosed.
  • specific examples of the specific heat-stable triazine skeleton-containing compound disclosed in the publication include melamine cyanurate, melamine phosphate, melam, melem, melon, succinoguanamine, melamine resin.
  • BT resin is listed. That is, it comprises the aminotriazine sulfate compound, the aminotriazine borate compound, the diaminotriazine borate compound, the triaminotriazine borate compound and the aminotriazine sulfamate compound used in the present invention.
  • a flame retardant resin composition comprising a vinyl aromatic resin, a polyphenylene ether resin, a phosphorus-containing compound, and a compound containing a triazine skeleton is used. It is disclosed in Japanese Patent Application Laid-Open No. 54-38348 and Japanese Patent Application Laid-Open No. 54-38349. However, the triazine skeleton compound disclosed as a specific example in each of these publications has improved moldability due to a low synergistic effect between the polyphenylene ether-based resin and the phosphorus-containing compound.
  • An object of the present invention is to provide a flame-retardant resin composition having a high degree of flame retardancy and excellent mechanical properties without using a specific nitrogen-containing compound and using a halogen-based flame retardant. It is intended to provide goods. Disclosure of the invention
  • the present invention is a.
  • Component (C) at least one member selected from the group consisting of an aminotriazine sulfate compound, an aminotriazine borate compound, a diaminotriazine borate compound, a triaminotriazine borate compound, and an aminotriazine sulfamate compound. 0.1 to 40 parts by weight of nitrogen-containing compound
  • the component (A) is a main component of the resin composition and plays a role of maintaining the strength of the resin composition.
  • Add (A 2) component of the present invention is a resin component for imparting a synergistic flame retardant component (B) and (C) components as well as impart heat resistance to it (A component is an optional component.
  • BEST MODE FOR CARRYING OUT THE INVENTION The components (B) and (C) of the present invention are main flame retardant components and are components for imparting flame retardancy to the component (A).
  • Resin (A) used in the present invention is an A alone or with A 2.
  • the rubber-modified styrene resin as the (A component) of the present invention refers to a rubber-based polymer in a copolymer matrix comprising a vinyl aromatic polymer or another vinyl monomer component copolymerizable therewith.
  • Specific examples of such components include impact-resistant polystyrene (HI resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and acrylonitrile-acryl.
  • Rubber-styrene copolymer (AAS resin) acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin) and the like.
  • the rubbery polymer needs to have a glass transition temperature (T g) of 0 ° C. or lower, more preferably ⁇ 30 ° C. or lower. If the T g of the rubbery polymer exceeds 0 ° C., the impact resistance is undesirably reduced.
  • T g glass transition temperature
  • examples of such rubbery polymers include gen-based rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), saturated rubber obtained by hydrogenating the gen rubber, isoprene rubber, Examples thereof include acryl-based rubbers such as chloroprene rubber and polybutyl acrylate, and ethylene-propylene-gen monomer terpolymer (EPDM). Particularly preferred are gen-based rubbers.
  • the content of the rubbery intermediate polymer in the component A is not particularly limited, but is preferably 1 to 60% by weight, and more preferably 5 to 25% by weight.
  • the content of the matrix resin portion is not limited, but is preferably in the range of 99 to 40% by weight, and more preferably in the range of 95 to 75% by weight. The balance between the impact resistance and the rigidity may be deteriorated.
  • the particle structure of the ( ⁇ ⁇ ) component rubbery polymer is not particularly limited. Typical examples include those having a structure and those having a single occlusion structure. Further, the rubber may have an average particle size distribution having a particle size distribution composed of two or more peaks of a small particle portion and a large particle portion without departing from the scope of the present invention.
  • a dry blend of the matrix resin portion and the rubbery polymer may be kneaded by a known kneader such as a Hensiel mixer, a Banbury mixer, a single screw extruder, or a twin screw extruder.
  • the particle size of the rubbery polymer in the component A is preferably from 0.1 to 5 mm in weight average particle size, more preferably from 0.5 to 4 / m, particularly preferably from 1 to 3. If the weight average particle diameter is out of the above range, not only the strength of the component A itself but also the strength of the street is lowered (the synergistic effect between the AJ resin and the components (B) and (C)). In order to achieve a high level of flame retardancy, a large amount of the component (B) and the component (C) must be blended, leading to a reduction in mechanical properties and moldability. Not preferred.
  • the weight average rubber particle diameter is within the above range, the synergistic effect of the coloring agent between the component and the component (C) on the coloring property can be increased, and a high level of flame retardancy and coloring and mechanical properties are balanced. It is preferable in taking the following.
  • the weight-average rubber particle diameter of the rubber-modified styrenic resin used herein refers to a matrix formed by mixing the rubber-modified styrenic resin pellets with a 50/50 volume% mixed solution of MEKZ acetone. After dissolving only the polystyrene portion to be dissolved, it is separated from the undissolved rubber particle portion by a centrifugal separator, and then dispersed in a DMF electrolyte solution at an appropriate concentration. It refers to the value measured using ( ⁇ type).
  • the gel content of the rubber-modified styrenic resin used as the AJ component is preferably from 20 to 80% by weight, more preferably from 22 to 60% by weight.
  • the gel content is within the above range, not only the impact strength of the AJ component itself is increased, but also the coloring property between the A component and the (C) component due to the coloring agent. High flame retardancy and coloring due to greater synergistic effect on This is preferable because the balance between the properties and mechanical properties is improved.
  • the gel content of the rubber-modified styrenic resin as used herein means that the rubber-modified styrenic resin pellet is dissolved in a 50/50 volume% mixed solution of MEKZ Acetone to dissolve only the polystyrene portion forming the matrix. After that, the undissolved rubber particles are separated by a centrifugal separator. This refers to the weight percent of the gel dried under reduced pressure at C and dried based on the original weight of the rubber-modified styrene resin.
  • the reduced viscosity (0.4 g / dl, toluene solution, 30.C measurement) which is a measure of the molecular weight of the rubber-modified styrenic resin used as the component A is from 0.3 to 1.2. It is preferably in the range of d 1 Zg, more preferably in the range of 0.5 to 1. O dl Zg
  • the reduced viscosity of the component is within the above range, the melt dripping property of the component (A) is reduced. Due to the decrease, the synergistic effect between (A) and (A 2 ), (B) and (C) increases, and (B) The amount of the component and the component (C) can be reduced, and the mechanical properties can be improved.
  • (A component of Merutofu port one rate rather preferably less 20 2 10 min, 15 gZl 0m in or less, more preferably less than l O gZl Om in. And particularly preferably not more than S gZl Om in.
  • (A L ) component is out of the above range, not only the moldability will deteriorate, but also the (A resin and (B) components In order to achieve a high level of flame retardancy, a large amount of the components (B) and (C) must be added, and the mechanical properties are reduced. Is not preferred.
  • the method for producing the component (A) is to add an aromatic vinyl monomer and, if necessary, other vinyl monomers copolymerizable therewith in the presence of the rubbery polymer described above. It can be obtained by known bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization
  • the aromatic vinyl monomer includes, in addition to styrene, ⁇ -methylstyrene, ⁇ -methyl- ⁇ -methyl ⁇ -alkyl-substituted styrenes such as styrene, ⁇ -methylstyrene, 0-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, and p-butyl styrene And one or more of these can be used.
  • unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.
  • an acrylate ester having an alkyl group having 1 to 8 carbon atoms can be used.
  • ⁇ -substituted maleimide monomers such as ⁇ -methylstyrene, acrylic acid, methacrylic acid, maleic anhydride, and ⁇ -phenylmaleimide are used. May be copolymerized.
  • the content of the other vinyl monomer copolymerizable with the aromatic vinyl monomer in the monomer mixture is 0 to 40% by weight.
  • ⁇ The amount of component A is determined according to the required mechanical strength, moldability, and heat resistance. Specifically, (Total amount of component AJ and optional component (A 2 ) is 100 It is preferable to mix 1 to 100 parts by weight, more preferably 40 to 95 parts by weight, and particularly preferably 60 to 90 parts by weight.
  • the polyphenylene ether resin blended as the component (A 2 ) in the present invention has the following general formula (I)
  • Q i to Q 4 are each independently selected from the group consisting of hydrogen and a hydrocarbon group, and m represents an integer of 30 or more.
  • polyphenylene ether-based resins include poly (2,6-dimethyl-1 ⁇ 4-phenylene) ether and poly (2,6—dimethyl-1 ⁇ 4-phenylene) ether.
  • polyphenylene ether-based resins are compatible with polystyrene-based resins at all compounding ratios.
  • the reduced viscosity (0.5 gZd1, chromate form solution, measured at 30 ° C.), which is a measure of the molecular weight of the polyphenylene ether resin used as the component (A 2 ) in the present invention, is 0.2. It is preferably in the range of -0.7 d1 Zg, more preferably in the range of 0.3-0.6 d1 Zg.
  • the reduced viscosity of the component (A 2 ) is within the above range, the moldability is improved and the balance of mechanical properties is excellent.
  • the amount of the component (A 2 ) is determined according to the required mechanical strength, moldability, and heat resistance. Specifically, (99 to 0 parts by weight, preferably 60 to 5 parts by weight, more preferably 40 to 100 parts by weight, based on 100 parts by weight of the total amount of the component A and the component (A 2 )) It is particularly preferred to mix by weight.
  • one or more phosphorus-containing flame retardants selected from organic phosphorus compounds and red phosphorus are used as the flame retardant of the component (B).
  • organic phosphorus-containing compound examples include phosphates typified by triphenylphosphine and phosphites typified by triphenylphosphite.
  • phosphates typified by triphenylphosphine
  • phosphites typified by triphenylphosphite.
  • the following general formulas (II) to (III) It is preferred that the compound has at least one structural unit represented by (V). 0
  • Ri to R 3 each represent a hydrocarbon residue, and di qs represents 0 or 1.
  • R 3 is — C (CH 3 ) 2 —, — CH 2 —, one S 0 2 —, one C 0 — and — 0 - represents a group selected from, R 6 to R 13 is a hydrogen atom or a hydrocarbon residue, ⁇ 1-0 7 is 0 or 1, n, is a number of polymerization degree of 1 to 30).
  • Ri ⁇ R 6 are each a hydrocarbon residue
  • R 7 to R 9 is a hydrogen atom, a halogen atom or a hydrocarbon residue, showing a (1 to 93 9 0 or 1.
  • organic phosphorus-containing compounds may be used alone or in combination of two or more.
  • organic phosphorus-containing compound triflatle phosphate, resorcinol bis (diphenyl phosphate) and the like are preferable.
  • red phosphorus used in the present invention those immediately after production by a usual method, those containing black phosphorus due to aging, untreated, inorganic and Z or organic or surface treated
  • red phosphorus obtained by adding yellow phosphorus and pulverizing may be used.
  • red phosphorus stabilized by surface treatment with inorganic and / or organic materials is preferably used in terms of safety and easy handling.
  • Examples of the surface-treated red phosphorus include: 1) aluminum hydroxide, magnesium hydroxide, magnesium carbonate, zinc carbonate, and hydrous aluminum gateate as disclosed in JP-A-59-170176. Those coated with a coating of an inorganic filler such as 2) the surface as disclosed in JP-A-51-109996 and JP-A-52-125489.
  • thermosetting resin Coated with thermosetting resin, 3) aluminum hydroxide, magnesium hydroxide, magnesium carbonate, zinc carbonate, hydrous Coated with a coating made of an inorganic filler such as aluminum formic acid and a thermosetting resin; 4) An inorganic filler such as aluminum hydroxide, magnesium hydroxide, magnesium carbonate, zinc carbonate, and hydrated aluminum gay acid Those coated twice with a thermosetting resin on the coating, and 5) those coated with a metal coating such as nickel after electroless plating of red phosphorus are preferably used. .
  • the average particle diameter of the red phosphorus used in the present invention is 50 m or less, preferably 0.01 to 30 ⁇ m, particularly preferably 0.01 to 30 ⁇ m, in order to obtain a molded article having a good glossy appearance. 0.1 to 15 m is preferred.
  • the amount of the component is determined according to the required flame retardancy and heat resistance. Specifically, it is necessary to add 0.1 to 30 parts by weight based on 100 parts by weight of the total of (A component or (A component and (A 2 ) component), and 3 to 25 parts by weight. More preferably, it is more preferably 5 to 20 parts by weight.
  • the component (C) of the present invention is a group consisting of an aminotriazine sulfate compound, an aminotriazine borate compound, a diaminotriazine borate compound, a triaminotriazine borate compound, and an aminotriazine sulfamate compound.
  • nitrogen-containing compound used in the present invention examples include melamine sulfate, melamine nitrate, melamine borate, dimelamine borate, melamine condensed borate, and melamine p-toluenesulfonate.
  • At least one nitrogen-containing compound selected from melamine sulfate, melamine borate, dimelamine borate, trimeramine borate and melamine sulfamate is preferred. It is preferable in terms of flame retardancy and economy. Of these, melamine sulfate is particularly preferred.
  • Amino triazine sulfate compounds used as the component (C) in the present invention have been described in Japanese Patent Application Laid-Open Nos. Sho 54-38348, 54-38349, 5-28719, and 5-33941.
  • Replacing with other aminotriazine compounds known in Japanese Patent Publication No. 7 causes problems such as 1) decrease in flame retardancy, 2) decrease in printability and paintability, thereby achieving the original object of the present invention. Not only is it not possible, but also problems such as a decrease in coloring properties due to a coloring agent and a decrease in mechanical properties occur.
  • the component (C) is pulverized to an average particle diameter of 50 ⁇ or less. Those are preferred. Furthermore, it is preferably from 0.01 to 30111, and particularly preferably from 0.1 to: L Om.
  • a suitable dispersing agent, a lubricant or the like may be blended during or after the pulverization treatment of the component (C) to prevent the finely pulverized product from reaggregating and coarsening.
  • a dispersant include white carbon, alkali metal stearate, and fatty acid amide.
  • re-agglomeration can be prevented by applying an appropriate surface treatment such as a force-braking agent treatment after the fine pulverizing treatment, and the compatibility with the resin can be promoted.
  • a surface treatment agent include a silane coupling agent, a titanium coupling agent, and an aluminum chelating agent.
  • the added amount of the component (C) is preferably 1 to 40 parts by weight, more preferably 3 to 25 parts by weight, based on 100 parts by weight of the total amount of the component (A) or the component (AJ) and the component (A 2 ). Parts by weight, particularly preferably 5 to 20 parts by weight.
  • the addition of the component (C) within the above range achieves the effect of making the resin flame-retardant and the effect of improving printing and coating properties. This is preferable in maintaining the balance between mechanical properties and mechanical properties.
  • (A 2) wherein in the case where the component as essential components, (C) by using a component, (A 2) flame retardant in the presence of component (B) and component synergistically composition
  • the purpose is to achieve high flame retardancy with low flame retardant addition and to provide high printability and paintability.
  • a styrene-based resin material a resin composition that imparts excellent printability and paintability without impairing the original performance and characteristics of the component A, and further provides the above-described high-level flame-retardant performance). it can.
  • the amount of the red phosphorus used as the component (B) is determined by the amount of the component and (C)
  • the amount is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, and most preferably 5 to 12 parts by weight based on 100 parts by weight of the total of the components. If the amount of the component (B) is less than 1 part by weight, the effect of flame retardation of the resin cannot be achieved, which is not preferable. On the other hand, when the amount exceeds 30 parts by weight, the flame retardancy is lowered and the physical properties of the resin composition are lowered, which is not preferable. In the present invention,
  • the amount of the nitrogen-containing compound used as the component (C) is preferably 0.1 to 30 parts by weight, more preferably 3 to 25 parts by weight, based on 100 parts by weight in total of the component A and the component (B). Parts, most preferably 5 to 20 parts by weight. However, if the amount is less than 0.1 part by weight, it is not preferable because the effect of flame retardation of the resin cannot be achieved. If the amount of the component (C) exceeds 30 parts by weight, the physical properties of the resin composition deteriorate, which is not preferable.
  • a dripping inhibitor (D) and a lubricant (E) can be blended.
  • the component (D) further improves the flame retardancy of the components (B) and (C) by preventing the drip of fire at the time of combustion. Also,
  • the component (D) is a component for improving the dispersibility of the component (C) of the present invention by micro-dispersing and exhibiting good mechanical properties.
  • the anti-drip agent used as the component (D) include a fluororesin, a silicone resin, polyphosphazene, and polyacrylonitrile. Preferred are fluorine-based resins and silicone resins, and particularly preferred are fluorine-based resins.
  • the fluororesin (D) used as an anti-dripping agent disperses in a fibril form to prevent drip of fire during combustion, and further improves the flame retardancy of component (B) and component (C).
  • the fluororesin may be any thermoplastic resin having a carbon-fluorine bond in the molecule, such as polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, or the like. Examples thereof include tetrafluoroethylene Z hexafluoropropylene copolymer and the like, and a mixture thereof. Polytetrafluoroethylene (PTFE) is most preferable. Further, these fluororesins can be easily produced by a known method, and can be easily obtained.
  • polytetrafluoroethylene can be obtained by using tetrafluoroethylene in an aqueous solvent using a free-radical catalyst (eg, sodium peroxydisulfate, potassium or ammonium) at a pressure of 100-1000 psi and 0-200 ° C. Is obtained by polymerizing at a temperature of 20 to 100 ° C. More details are disclosed in U.S. Pat. No. 2,393,967 to Bruker. Although not essential, it is preferable to use a resin in a state of relatively large particles, for example, particles having an average particle diameter of 0.3 to 0.7 mm (mainly 0.5 mm).
  • a free-radical catalyst eg, sodium peroxydisulfate, potassium or ammonium
  • Such a suitable polytetrafluoroethylene is called type 3 according to ASTM.
  • Component (D) is used in an amount of 0 to 5 parts by weight, based on a total of 100 parts by weight of (AJ component, (A 2 ) component, (B). Component, and (C) component). 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight, particularly preferably 0.05 to 0.5 part by weight The amount of component (D) exceeds 5 parts by weight. This is not preferred because it results in an economically expensive resin, difficulties in extrusion kneading, and a decrease in the physical properties of the resin composition.
  • the component (E) is a component for improving the moldability of the present invention by improving the fluidity while maintaining the flame retardancy and the heat resistance. It is a component for improving the dispersibility of the component (C) of the present invention by plasticizing the resin of the component to exhibit good mechanical properties.
  • the lubricant used as the component (E) include higher fatty acid amide compounds, higher fatty acids, higher fatty acid ester compounds, higher aliphatic alcohols, and metal stones. Preferred are higher fatty acid amide compounds and higher fatty acid ester compounds.
  • the amount of the component (E) used is 0 to 5 parts by weight, preferably 0 to 3 parts by weight, based on 100 parts by weight of the total of the component, the component (A 2 ), the component (B), and the component (C). Parts by weight. If the amount of the component (E) exceeds 5 parts by weight, the fluidity of the resin composition is remarkably reduced and the cost of the composition is undesirably increased.
  • the flame-retardant resin composition of the present invention is obtained by weighing (A, (A 2 ), (B), (C) and other components described above so as to have a predetermined mixing ratio, and mixing them uniformly.
  • the mixing method is not particularly limited, but it can be produced by a usual method, for example, melt blending by kneading with an extruder, etc.
  • the flame-retardant resin composition of the present invention may contain an organic phosphite compound as needed, as long as the effects of the present invention are not impaired.
  • additives such as antistatic agents, antioxidants, ultraviolet absorbers, coloring agents, surface modifiers, dispersants, plasticizers, organotin compounds, light stabilizers, processing aids, A foaming agent, an inorganic filler such as glass fiber and talc, and the like can be added.
  • thermoplastic resin or a thermosetting resin other than the component A can be added to the flame-retardant resin composition of the present invention, if desired, as long as the effects of the present invention are not impaired.
  • the obtained flame-retardant resin composition of the present invention is prepared by using a usual thermoplastic resin molding method, for example, injection molding, extrusion molding, compression molding, or the like, to obtain flame retardancy, mechanical properties, and water resistance.
  • a thermoplastic resin molding method for example, injection molding, extrusion molding, compression molding, or the like.
  • HIPS High Impact Strength Polystyrene
  • ABS (Acrylonitril-Butadiene-Styrene-Resin) L ⁇ 0 [HIPS-a]: Rubber content: 9.3 wt%,
  • Weight average rubber particle diameter 2.3 // m
  • Weight average rubber particle size 1.2 im
  • Weight average rubber particle diameter 1.4 zm
  • Weight average rubber particle diameter 2.7 / m
  • Weight average rubber particle diameter 0.5 // m
  • Resin coating amount 25%,
  • (C) Component The following components were used.
  • Trimeramine borate] Average particle size: 7 m
  • Component (D) The following polytetrafluoroethylene (PTFE) was used as the fluororesin.
  • PTFE polytetrafluoroethylene
  • Weight-average rubber particle diameter A rubber-modified styrenic resin pellet was dissolved in a 50/50% by volume mixed solution of MEKZ acetate to dissolve only the polystyrene portion forming matrix. The undissolved rubber particles are separated by a centrifugal separator, and then dispersed in a DMF (N, N-dimethylformamide) electrolyte solution at an appropriate concentration. (Riser type 1).
  • the weather resistance was evaluated by a test method based on JIS K 7102.
  • the black panel temperature is 55 as a weather resistance tester.
  • ⁇ The printed surface slightly peels off.
  • X The printed surface peels over a wide area.
  • the coloring property was evaluated by visually observing the coloring property of a molded product obtained by adding 1 part by weight of a dark blue colorant to 100 parts by weight of the resin composition and judging according to the following criteria.
  • (C) Ingredient Melamine sulfate a (15 parts by weight) After dry blending 20 parts by weight, using a 30 mm 0- twin screw extruder manufactured by Ikegai Ironworks Co., Ltd. at a cylinder temperature of 220 ° C By kneading under the conditions, a pellet of the target styrene-based flame-retardant resin composition was obtained. After the obtained pellets were pre-dried, test specimens were prepared using a 40 t injection molding machine manufactured by Nissei Plastics Co., Ltd., and flame retardancy, Izod impact value, flexural modulus, flexural strength, glossiness were measured. , Weather resistance and mold contamination were evaluated.
  • Example 1 the same experiment as in Example 1 was repeated, except that polytetrafluoroethylene PTF E-a and the lubricant (a) of the component (E) were additionally added as the component (D). Table 1 shows the results.
  • Example 1 the same experiment as in Example 1 was carried out except that melamine borate shown in Table 1 was used instead of melamine sulfate, or PTF E-a and a lubricant were additionally added. Repeated. Table 1 shows the results. ⁇ table 1 ⁇
  • Example 1 the same experiment as in Example 1 was repeated except that melamine or melamine cyanurate was used in place of melamine sulfate (C) component. Table 2 shows the results.
  • Example 1 was the same as Example 1 except that the types and amounts of the components (B) and (C) were as shown in Table 3 and the components (D) and (E) were added. The same experiment was repeated. Table 3 shows the results. (Table 3)
  • Example 1 components (B), (C), and (D) and (E) were used in the same manner as in Example 1 except that the types and amounts of the components were changed to those shown in Table 4. The same experiment was repeated. Table 4 shows the results. (Table 4)
  • Example 1 (the same experiment as in Example 1 was repeated except that the rubber-modified styrenic resin shown in Table 5 was used as the component A and the components (D) and (E) were added.
  • Table 5 shows the results. (Table 5)
  • Example 1 the same experiment as in Example 1 was repeated except that (C) the types and amounts of the components were as shown in Table 6 and the (D) and (E) components were added.
  • Figure 6 shows the results.
  • Example 1 In Example 1, the same as Example 1 except that the kind and the amount of the component (C) were the melamine cyanurate and the amount of the compound shown in Table 6, and the components (D) and (E) were added. The experiment was repeated.
  • Example 1 melamine cyanurate was used in place of the component (C).
  • component (D) was added, and other components such as polyphenylene ether, an organic phosphorus compound, and a higher fatty acid amide compound were added in the proportions shown in Table 4. Repeated.
  • Table 7 shows the results. In Table 7, the following were used for polyphenylene ether-1a, organic phosphorus compound-1a, and higher fatty acid amide compound-1a, respectively. Table 7 shows the results.
  • polyphenylene ether having a reduced viscosity of 0.55 dl Zg and polystyrene are mixed at a weight ratio of 70/30 and kneaded in advance with a twin screw extruder. This is referred to as polyphenylene ether-a.
  • An organic phosphorous compound consisting of diphenylresorcinyl phosphate, triphenyl phosphate and an aromatic condensed phosphate ester, and is composed of diphenylresorcinyl phosphate and triphenyl phosphate.
  • organophosphorus compound 1a The organophosphorus compound which is 2/1 8.3 / 37.5 was designated as organophosphorus compound 1a.
  • Example 7 melamine cyanurate was used in place of component (C), component (D) was added, and as other components, organophosphorus compounds and higher fatty acid amide compounds are shown in Table 7. The same experiment as in Example 1 was repeated, except that the components were blended at the following ratios. Table 7 shows the results. In Table 7, the same organic phosphorus compound-a and higher fatty acid amide compound-a as those used in Comparative Example 7 were used.
  • Example 21 (the same experiment as in Example 1 was repeated except that the rubber-modified styrenic resin shown in Table 8 was used as the A component and PTFE-a was additionally added. The results are shown. (Example 21)
  • Example 1 the same experiment as in Example 1 was repeated, except that melamine sulfamate was used instead of melamine sulfate as the component (C) and PTFE-a was additionally added. Table 8 shows the results.
  • Rubber-modified styrenic resin g Rubber content 9.2% by weight
  • the following polyphenylene ether resin was used as the polyfumonylene ether (PPE) resin of the component (A 2 ).
  • Polyphenylene ether-b (PPE) resin Poly (2,6-dimethyl-1--1,1) having a reduced viscosity sc of 0.54 in a chloroform solution of 0.5 g, dl at 30 ° C. 4—Phenylene ether)
  • Flame retardant 1 c Red Lin (equivalent to the above-mentioned Red Lin a), fuanol resin coated product, resin coat amount: 15%, average particle size: 10 to 15
  • Triazine compound a Melamine sulfate (equivalent to the above-mentioned melamine sulfate c), average particle size: 15 m
  • Triazine compound 1b Melamine sulfate, average particle size: 15 ⁇ m, treated with silane coupling agent (a-aminobutyral pill-triethoxysilane, 2%)
  • Triazine compound 1c Melamine sulfate (the above sulfuric acid Melamine-a equivalent), average particle size: 3 m
  • Triazine compound d Benzoguanamine sulfate, average particle size: 15 m
  • Anti-dripping agent a: Teflon 6—J, manufactured by Mitsui Dupont Fluorochemicals, Inc.
  • the following lubricant was used as the lubricant of the component (E).
  • Lubricant b Ethylene bisstearic acid amide
  • Tables 1 to 4 Each of the components shown in Tables 1 to 4 was subjected to a cylinder temperature of 220 to 280 using a 3 O mm — twin screw extruder manufactured by Ikegai Iron Works, Ltd. By kneading under the conditions of C, a pellet of the target styrene-based resin composition was obtained. After the obtained pellets were pre-dried, test specimens were prepared using a 100 t injection molding machine manufactured by Nippon Steel Works Co., Ltd. and a 40 t injection molding machine manufactured by Nissei Plastics Co., Ltd. Paintability, colorability, Izod impact value, and flame retardancy were evaluated. Tables 9 to 12 show the results.
  • Styrene resin-g 60 parts by weight 60 parts by weight 60 parts by weight 60 parts by weight 60 parts by weight
  • Triazine compound a 6 parts by weight
  • Example 1 24 Example 1 25
  • Example 1 26
  • Lubricant b Printing / paintability ⁇ ⁇ ⁇ Coloring ⁇ ⁇ ⁇ Izod impact value
  • P PE resin b 40 parts by weight 30 parts by weight 25 parts by weight 30 parts by weight D J fiX sword
  • Flame retardant 1 b 15 parts by weight 15 parts by weight 10 parts by weight 13 parts by weight Flame retardant 1 c
  • Anti-dripping agent a 0.1 parts by weight
  • the resin composition of the present invention has high flame retardancy without using a halogen-based flame retardant, and has excellent effects in mechanical properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur une composition de résine styrénique dont les propriétés ignifuges sont remarquablement améliorées sans recourir à des agents ignifuges halogénés et dont les propriétés mécaniques sont excellentes. Ladite composition comprend: (A) 100 parties en poids d'une résine styrénique modifiée par caoutchouc (A1) ou d'un mélange de la résine (A1) avec une résine de polyphène éther (A2), (B) de 0,1 à 30 parties en poids d'au moins un agent ignifuge phosphoré sélectionné parmi des composés organophosphorés ou du phosphore rouge, et (C) de 0,1 à 40 parties en poids d'au moins un composé azoté choisi dans un groupe consistant en aminotriazine sulfate, aminotriazine borate, diaminotriazine borate, triaminotriazine borate et aminotriazine sulfamate.
PCT/JP1996/001943 1995-07-14 1996-07-12 Composition ignifuge a base de resines WO1997004028A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP17917495A JPH0931293A (ja) 1995-07-14 1995-07-14 難燃性スチレン系樹脂組成物
JP7/179174 1995-07-14
JP7/288846 1995-11-07
JP28884695A JPH09132693A (ja) 1995-11-07 1995-11-07 難燃性樹脂組成物

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WO1997004028A1 true WO1997004028A1 (fr) 1997-02-06

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5447750A (en) * 1977-08-30 1979-04-14 Ici Ltd Flameeretardant polyamide composition
JPH01234464A (ja) * 1988-01-23 1989-09-19 Ciba Geigy Ag 煤煙及び有毒ガス抑制組成物
EP0389768A2 (fr) * 1989-03-29 1990-10-03 V.A.M.P. S.r.l. Composition retardatrice de flamme et à émission de fumée limitée pour polymères et matériaux polymères ainsi obtenus
JPH0425543A (ja) * 1990-05-22 1992-01-29 Asahi Chem Ind Co Ltd 難燃性樹脂組成物
JPH05117485A (ja) * 1991-10-30 1993-05-14 Asahi Chem Ind Co Ltd 優れた難燃性を有するスチレン系耐衝撃性樹脂組成物
JPH05117486A (ja) * 1991-10-30 1993-05-14 Asahi Chem Ind Co Ltd 難燃耐熱耐衝撃性樹脂組成物
JPH05287119A (ja) * 1992-04-09 1993-11-02 Asahi Chem Ind Co Ltd 外観の優れた難燃性樹脂組成物
JPH05339417A (ja) * 1992-06-10 1993-12-21 Asahi Chem Ind Co Ltd 低揮発性難燃耐熱耐衝撃性樹脂組成物
JPH07165982A (ja) * 1993-10-22 1995-06-27 Mitsui Toatsu Chem Inc 難燃剤組成物とそれを用いた難燃性樹脂組成物
JPH0848812A (ja) * 1994-08-05 1996-02-20 Tokuyama Corp 難燃性樹脂組成物
JPH0881583A (ja) * 1994-09-13 1996-03-26 Tokuyama Corp 難燃性樹脂組成物

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5447750A (en) * 1977-08-30 1979-04-14 Ici Ltd Flameeretardant polyamide composition
JPH01234464A (ja) * 1988-01-23 1989-09-19 Ciba Geigy Ag 煤煙及び有毒ガス抑制組成物
EP0389768A2 (fr) * 1989-03-29 1990-10-03 V.A.M.P. S.r.l. Composition retardatrice de flamme et à émission de fumée limitée pour polymères et matériaux polymères ainsi obtenus
JPH0425543A (ja) * 1990-05-22 1992-01-29 Asahi Chem Ind Co Ltd 難燃性樹脂組成物
JPH05117485A (ja) * 1991-10-30 1993-05-14 Asahi Chem Ind Co Ltd 優れた難燃性を有するスチレン系耐衝撃性樹脂組成物
JPH05117486A (ja) * 1991-10-30 1993-05-14 Asahi Chem Ind Co Ltd 難燃耐熱耐衝撃性樹脂組成物
JPH05287119A (ja) * 1992-04-09 1993-11-02 Asahi Chem Ind Co Ltd 外観の優れた難燃性樹脂組成物
JPH05339417A (ja) * 1992-06-10 1993-12-21 Asahi Chem Ind Co Ltd 低揮発性難燃耐熱耐衝撃性樹脂組成物
JPH07165982A (ja) * 1993-10-22 1995-06-27 Mitsui Toatsu Chem Inc 難燃剤組成物とそれを用いた難燃性樹脂組成物
JPH0848812A (ja) * 1994-08-05 1996-02-20 Tokuyama Corp 難燃性樹脂組成物
JPH0881583A (ja) * 1994-09-13 1996-03-26 Tokuyama Corp 難燃性樹脂組成物

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