JP5048268B2 - Flame retardant conductive thermoplastic resin composition - Google Patents

Description

  The present invention relates to a flame-retardant conductive thermoplastic resin that does not contain bromine, a chlorine-based flame retardant, and an antimony compound and is excellent in bleed-out resistance, flame retardancy, and conductivity.

  Thermoplastic resins are widely used in electrical and electronic parts, automobile parts and the like because of their excellent characteristics. In recent years, particularly in home appliances, electricity, and OA-related parts, in order to ensure safety against fire, there are many examples that require high flame retardancy, and therefore, various flame retardant blends have been studied.

  When imparting flame retardancy to thermoplastic resins, it is common to use halogen-based flame retardants as flame retardants, and use flame retardant aids such as antimony trioxide as needed to achieve advanced flame retardants. A resin composition having an effect and excellent mechanical strength, heat resistance and the like has been obtained. Recently, however, regulations on halogenated flame retardants are being issued mainly for products for overseas markets, and non-halogenated flame retardants are being studied.

  For example, Patent Document 1 discloses a technique related to a resin composition comprising an organic phosphorus flame retardant having the same structure as the present invention and a thermoplastic resin, and a compression of 3.2 mm thickness using a polybutylene terephthalate resin. It is described that in a molded product, flame retardancy of V-1 to V-0 can be realized on the basis of UL94.

  However, in recent years, particularly for home appliances, electricity and OA-related parts, flame retardancy and conductivity are required, and long-term reliability of products is regarded as important. In particular, when it is forced to be used for a long time in a high temperature environment, the flame retardant bleeds out of the product due to heat. As a result, the initial flammability is changed and lowered, and the conductivity is also lowered and impaired, which is strongly desired to be improved. These requirements cannot be solved by the prior art, and there is no satisfactory one at present.

JP-A-53-128195

  In view of the current situation as described above, an object of the present invention is to provide a flame retardant conductive thermoplastic resin composition that can maintain excellent flame retardancy and conductivity even when used for a long time in a high temperature environment. It is what.

  As a result of intensive studies in order to achieve the above object, the present inventors have determined that an organophosphorus flame retardant (B) and a conductive carbon compound (C) having a specific structure are added to the thermoplastic resin (A). By containing it at a specific ratio, a flame-retardant conductive thermoplastic resin composition that has excellent flame retardancy and conductivity, and can maintain initial characteristics even after heating by suppressing the bleed-out of the flame retardant, is completed. It came to.

  That is, the present invention relates to the following general formula (1) with respect to 100 parts by weight of the thermoplastic resin (A):

It relates to a flame-retardant conductive thermoplastic resin composition containing 10 to 80 parts by weight of the organic phosphorus flame retardant (B) and 0.1 to 20 parts by weight of a conductive carbon compound (C).

It is preferable that the thermoplastic resin composition satisfies the following conditions (a) and (b).
(A) In a molded product having a thickness of 3.2 mm, a length of 127 mm, and a width of 12.7 mm, the initial flammability is V-0 to V-2 based on UL94, and combustion after heat treatment at 190 ° C. for 500 hours The property is the same as the initial combustibility.
(B) The ratio (R ₁₀₀ / R _i ) of the value (R ₁₀₀ ) after 190 hours at 190 ° C. to the initial value (R _i ) of the surface specific resistance value is 100 or less.

  The thermoplastic resin (A) is preferably at least one selected from polyester resins, polycarbonate resins, polyamide resins, polyphenylene ether resins, and polyolefin resins.

  Moreover, this invention relates to the resin molding containing the flame-retardant conductive thermoplastic resin composition in any one of the said.

  The flame retardant conductive thermoplastic resin composition of the present invention improves the bleed-out suppression of the flame retardant, and can maintain excellent flammability and conductivity even when the molded body is exposed to high temperature. It can be suitably used as a molding material for electrical, OA parts, etc., and is industrially useful.

  In the present invention, 10 to 80 parts by weight of the organophosphorus flame retardant (B) represented by the general formula (1) and 0. 0 parts of the conductive carbon compound (C) with respect to 100 parts by weight of the thermoplastic resin (A). The present invention relates to a flame retardant conductive thermoplastic resin composition containing 1 to 20 parts by weight.

  Examples of the thermoplastic resin (A) used in the present invention include polyester resins, polycarbonate resins, polyamide resins, polyphenylene ether resins, and polyolefin resins.

  Polyester resins are divalent acids such as terephthalic acid as acid components or derivatives thereof having ester forming ability, glycols having 2 to 10 carbon atoms as glycol components, and other divalent alcohols or ester forming ability. The saturated polyester resin obtained using those derivatives etc. which have. Among these, a polyalkylene terephthalate resin is preferable in that it has an excellent balance of processability, mechanical properties, electrical properties, heat resistance, and the like. Specific examples of the polyalkylene terephthalate resin include polyethylene terephthalate resin, polybutylene terephthalate resin, and polyhexamethylene terephthalate resin. Among them, polyethylene terephthalate resin is particularly preferable because of excellent heat resistance and chemical resistance. .

  In the polyester resin used as the thermoplastic resin (A) in the present invention, if necessary, when the polyester resin is 100 parts by weight, preferably 20 parts by weight or less, particularly preferably 10 parts by weight or less, Other components can be copolymerized. As the copolymer component, known acid components, alcohol and / or phenol components, or derivatives thereof having an ester forming ability can be used.

  Examples of the copolymerizable acid component include a divalent or higher aromatic carboxylic acid having 8 to 22 carbon atoms, a divalent or higher aliphatic carbonic acid having 4 to 12 carbon atoms, and a divalent or higher carbon number. Examples thereof include 8 to 15 alicyclic carboxylic acids and derivatives thereof having ester forming ability. Specific examples of copolymerizable acid components include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carbodiphenyl) methaneanthracene dicarboxylic acid, 4,4′-diphenylcarboxylic acid, 1,2-bis. (Phenoxy) ethane-4,4′-dicarboxylic acid, 5-sodium sulfoisophthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, maleic acid, trimesic acid, trimellitic acid, pyromellitic acid, 1,3 -Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and derivatives thereof having ester forming ability. These are used alone or in combination of two or more. Among these, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are preferable because the resulting resin is excellent in physical properties, handling properties, and ease of reaction.

  Examples of the copolymerizable alcohol and / or phenol component include dihydric or higher aliphatic alcohols having 2 to 15 carbon atoms, dihydric or higher alicyclic alcohols having 6 to 20 carbon atoms, and 6 to 40 carbon atoms. Examples thereof include aromatic alcohols having a valence of 2 or more, phenols, and derivatives thereof having ester forming ability.

  Specific examples of the copolymerizable alcohol and / or phenol component include ethylene glycol, propanediol, butanediol, hexanediol, decanediol, neopentylglycol, cyclohexanedimethanol, cyclohexanediol, 2,2′-bis (4 -Hydroxyphenyl) propane, 2,2'-bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and the like, and derivatives having ester forming ability, and cyclic esters such as ε-caprolactone It is done. Among these, ethylene glycol and butanediol are preferable because they are excellent in physical properties, handleability, and reaction ease.

  Furthermore, some polyalkylene glycol units may be copolymerized. Specific examples of the polyalkylene glycol include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and random or block copolymers thereof, alkylene glycols of bisphenol compounds (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, And a modified polyalkylene glycol such as an adduct or the like. Among these, bisphenol A having a molecular weight of 500 to 2,000 is preferable because the heat stability during copolymerization is good and the heat resistance of the molded product obtained from the resin composition of the present invention is hardly lowered. Polyethylene glycol adducts are preferred. These polyester resins may be used alone or in combination of two or more.

  The method for producing the thermoplastic polyester resin in the present invention can be obtained by a known polymerization method such as melt polycondensation, solid phase polycondensation, solution polymerization and the like. In order to improve the color of the resin during polymerization, phosphoric acid, phosphorous acid, hypophosphorous acid, monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, methyl diethyl phosphate, triethyl phosphate, triisopropyl phosphate One or more compounds such as tributyl phosphate and triphenyl phosphate may be added.

  Further, in order to increase the crystallinity of the obtained thermoplastic polyester resin, various organic or inorganic crystal nucleating agents generally well known at the time of polymerization may be added alone or in combination of two or more. May be.

  The intrinsic viscosity of the thermoplastic polyester resin used in the present invention (measured at 25 ° C. in a mixed solution of phenol / tetrachloroethane of 1/1 by weight) is preferably 0.4 to 1.2 dl / g, 0 More preferably, it is 6 to 1.0 dl / g. If the intrinsic viscosity of the thermoplastic polyester resin is less than 0.4 dl / g, the mechanical strength and impact resistance tend to decrease, and if it exceeds 1.2 dl / g, the fluidity during molding tends to decrease.

  The polyamide resin used as the thermoplastic resin (A) in the present invention is a polymer that contains an amide bond (—NHCO—) in the main chain and can be melted by heating. Specific examples include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodeca Mido (nylon 612), polyundecane methylene adipamide (nylon 116), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytrimethylhexamethylene terephthalamide (nylon TMHT), polyhexamethylene isophthalamide (Nylon 6I), polyhexamethylene terephthalate / isophthalamide (nylon 6T / 6I), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-4-aminocyclohexane) Syl) methane dodecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (nylon MXD6), polyundecamethylene terephthalamide (nylon 11T), polyundecamethylene hexahydroterephthalamide (nylon 11T (H)), and These copolyamides and mixed polyamides are available. Among these, nylon 6, nylon 46, nylon 66, nylon MXD6, nylon 11, nylon 12 and their copolymerized polyamides and mixed polyamides are preferable, and nylon 6, nylon is particularly preferable in terms of strength, elastic modulus, cost, and the like. 66, nylon 46 and nylon MXD6 are preferably used. Aromatic polyamide resins may also be used. Although there is no restriction | limiting in particular in the molecular weight of these polyamide resins, Usually, the thing of the range whose relative viscosity measured in 25 degreeC concentrated sulfuric acid is 0.5-5.0 is used preferably. If the relative viscosity is less than 0.5, the mechanical strength tends to decrease, and if it exceeds 5.0, the fluidity during molding tends to decrease.

  The above polyamide resins may be used alone or in combination of two or more of those having different compositions or components and / or different relative viscosities.

  The polycarbonate resin used as the thermoplastic resin (A) in the present invention is not particularly limited, and includes any of aliphatic, alicyclic, and aromatic polycarbonates. Among them, aromatic polycarbonates are preferable. Aromatic polycarbonates are produced by reacting one or more bisphenols that may contain polyhydric phenols with carbonates such as bisalkyl carbonates, bisaryl carbonates, and phosgene. Specific examples of bisphenols include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, and 2,2-bis. (4-hydroxyphenyl) propane, ie bisphenol A, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl)- 3-methylbutane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1, 1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxy-3-methylphenyl) methane, bis 4-hydroxy-3-methylphenyl) phenylmethane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2- Bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (4-hydroxy-3-sec-butylphenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylpropane, bis (4-hydroxyphenyl) Diphenylmethane, bis (4-hydroxyphenyl) dibenzylmethane, 4,4'-dihydroxydiphenylamine Le, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, phenolphthalein and the like. The most typical of these is bisphenol A.

  Although there is no limitation on the production method of the polycarbonate resin used in the present invention, an organic solvent that dissolves the produced polymer, an alkaline water, and an alkali metal salt of bisphenols and a carbonic acid ester derivative active in nucleophilic attack. Interfacial polymerization method in which polycondensation reaction is performed at the interface of bisphenols and pyridine method in which polycondensation reaction is carried out in an organic base such as pyridine using bisphenols and carbonate derivatives active in nucleophilic attack, bisphenols and bisalkyl carbonates, A transesterification method is generally known in which a carbonate such as bisaryl carbonate is used as a raw material and a polycarbonate is produced by a transesterification reaction. Examples of the carbonic acid ester derivative active in nucleophilic attack used in the interfacial polymerization method and the pyridine method include phosgene and carbodiimidazole. Among them, phosgene is generally available because of its availability. Specific examples of the carbonic acid ester used in the transesterification method include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate and the like as bisalkyl carbonate, diphenyl carbonate as bisaryl carbonate, Bis (2,4-dichlorophenyl) carbonate, bis (2,4,6-trichlorophenyl) carbonate, bis (2-nitrophenyl) carbonate, bis (2-cyanophenyl) carbonate, bis (4-methylphenyl) carbonate, Bis (3-methylphenyl) carbonate, dinaphthyl carbonate, etc. are mentioned. Among these, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate are most preferably used because of easy availability of raw materials and easy reaction.

  Although there is no restriction | limiting in particular in the molecular weight of polycarbonate resin used by this invention, For example, the weight average molecular weight Mw measured at 40 degreeC in the gel permeation chromatography (GPC) by tetrahydrofuran (THF) solvent is single molecular weight dispersion | distribution polystyrene conversion And 15,000 to 80,000, preferably 30,000 to 70,000. If the Mw is less than 15,000, the mechanical properties and impact resistance of the resulting molded product tend to be low, and if it is greater than 80,000, there is a problem in workability such as fluidity during molding. Tend to occur.

  The polyphenylene ether resin used as the thermoplastic resin (A) in the present invention is the following general formula (2):

(Wherein R ¹ , R ² , R ³ and R ⁴ are each substituted with hydrogen, a halogen atom, an alkyl group which may be substituted with a functional group, an aralkyl group which may be substituted with a functional group, or a functional group. An aryl group which may be substituted, or an alkoxy group which may be substituted with a functional group). Here, examples of the functional group include a carboxyl group, a hydroxyl group, and an amino group.

  Specific examples of the polyphenylene ether homopolymer include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6 -Diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether Poly (2-ethyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloro-1) , 4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether Le, and the like.

  The above polyphenylene ether resins can be used singly or in combination of two or more types having different compositions or components and / or different molecular weights.

  The polyolefin resin used as the thermoplastic resin (A) in the present invention is not particularly limited, and a homopolymer of α-olefin, a copolymer of these α-olefins, or these α-olefins as a main component and necessary. And a copolymer having another unsaturated monomer as a subcomponent. Here, the copolymer may be any type of copolymer such as block, random, graft, or a combination thereof.

  Examples of the α-olefin include ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, heptene-1, octene-1, and the like. The thing of 2-8 is preferable. Further, the unsaturated monomer is, for example, (meth) acrylic acid, (meth) acrylic acid ester, unsaturated organic acid such as maleic acid or the like, ester, anhydride, unsaturated aliphatic cyclic olefin, etc. Is mentioned. Specific examples of these polyolefins include low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polybutene, polyisobutylene, poly-4-methyl-pentene-1, ethylene-propylene random or block copolymer, ethylene-butene. A copolymer, an ethylene-propylene-diene copolymer, etc. are mentioned. Among them, polypropylene is preferable.

  In addition, these olefin polymers may be introduced with functional groups such as chlorine, sulfonyl group, carboxyl group, ester group, epoxy group, acid anhydride group, among others, among which carboxyl group, epoxy group, An acid anhydride group is preferable from the viewpoint of improving the dispersibility of the silane clay composite and the physical properties of the obtained molded product. The method for introducing the functional group is not particularly limited, and examples thereof include unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid; unsaturated carboxylic acid anhydrides such as itaconic anhydride, maleic anhydride and citraconic anhydride. And one or more selected from the group consisting of epoxy group-containing unsaturated compounds such as glycidyl methacrylate and allyl glycidyl ether, polyolefin resin and organic oxide are thoroughly mixed, and then melt-kneaded using an extruder or the like. Can be obtained.

  The organic oxide preferably has a half-life of 1 minute of 100 ° C. or higher, more preferably 130 ° C. or higher. Specifically, dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide; diacyl peroxides such as acetyl peroxide, di-i-propyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, etc. Peroxy dicarbonates; peroxyesters such as t-butyl peroxypivalate and t-butyl peroxylaurate; ketone peroxides such as methyl ethyl ketone peroxide; 1,1-bis-t-butylperoxycyclohexane, 2 Peroxyketals such as 2-bis-t-butylperoxyoctane; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; azo compounds such as 2,2-azo-i-butyronitrile Is .

  The organophosphorus flame retardant (B) used in the present invention is the following general formula (1):

It is represented by The lower limit of the repeating unit n is n = 2, preferably n = 3, and particularly preferably n = 5. If it is less than n = 2, there is a tendency that the crystallization of the polyester resin is inhibited or the mechanical strength is lowered. There is no particular limitation on the upper limit of the repeating unit n, but if the molecular weight is excessively increased, the dispersibility and the like tend to be adversely affected. Therefore, the upper limit value of the repeating unit is n = 20, preferably n = 15, and particularly preferably n = 13.

  The manufacturing method of the organophosphorus flame retardant (B) used in the present invention is not particularly limited, and is obtained by a general polycondensation reaction. For example, it can be obtained by the following method.

  That is, the following general formula (3):

9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide represented by the following formula: an equimolar amount of itaconic acid and two or more moles of ethylene glycol with respect to itaconic acid; A phosphorus-based flame retardant solution is obtained by heating and stirring at 120 to 220 ° C. in a gas atmosphere. To the obtained phosphoric flame retardant solution, antimony trioxide and zinc acetate were added, and the temperature was further maintained at about 220 ° C. under a vacuum of 1 Torr (= 1.33 × 10 ² Pa) or less. The polycondensation reaction is conducted while distilling off. After about 5 hours, the reaction is considered to be complete when the distillate of ethylene glycol has decreased extremely. Under these conditions, the organic phosphorus flame retardant (B) can be obtained because it is a solid having a molecular weight of 4000 to 12000 and the phosphorus content is about 8% by weight.

  The organophosphorus flame retardant (B) content in the flame-retardant conductive thermoplastic resin composition of the present invention is preferably 10 parts by weight as a lower limit with respect to 100 parts by weight of the thermoplastic polyester resin, and 20 parts by weight. Is more preferable, and 30 parts by weight is even more preferable. When the lower limit of the content of the organophosphorus flame retardant (B) is less than 10 parts by weight, the flame retardancy tends to decrease. The upper limit of the organophosphorus flame retardant (B) content is preferably 80 parts by weight, and more preferably 70 parts by weight. If the upper limit of the content of the organophosphorous flame retardant (B) exceeds 80 parts by weight, the mechanical strength tends to decrease and the moldability tends to deteriorate.

  In this invention, electroconductivity can be provided to a flame-retardant thermoplastic resin composition by containing a conductive carbon compound (C) further.

The conductive carbon compound (C) in the present invention is not particularly limited, and commercially available granular, fibrillar, fibrous, and scale-like compounds can be used. Examples of the granular carbon compound include acetylene black and various types of furnace conductive carbon black, and various commercially available ones can be used. For example, as a granular example, trade name Ketjen Black (registered trademark) manufactured by Ketjen Black International Co., Ltd., trade name HOP manufactured by Nippon Graphite Industry Co., Ltd., and the like can be given. As an example of a fibrous form, trade name Pyrofil manufactured by Mitsubishi Rayon Co., Ltd. may be mentioned. Examples of the fine fibrillar carbon compound include a fine fibrillar carbon compound having a diameter of about 3.5 nm to 75 nm, which is referred to as a so-called carbon nanotube, and various commercially available ones. Can be used. For example, trade name Hyperion manufactured by Hyperion Catalysis International Co., Ltd. may be mentioned. Moreover, as an example of a fibrous thing, the vapor phase carbon fiber VGCF by Showa Denko KK is mentioned. As described above, the type of the carbon compound in the present invention has a diameter of 1 μm among granular, fibril, and fiber shapes from the viewpoint of importance of the surface property of the molded product and the prevention of particle dropout from the molded product. Those having a length of 50 μm or less are preferred. These may be used alone or in combination of two or more.

  The lower limit of the weight ratio of the conductive carbon compound (C) used in the thermoplastic resin composition of the present invention is preferably 0.1 parts by weight, more preferably 2 parts by weight, and even more preferably 5 parts by weight. The upper limit is preferably 20 parts by weight, more preferably 15 parts by weight, and even more preferably 10 parts by weight. If the lower limit of the carbon compound is less than 0.1 parts by weight, the conductivity may be insufficient, and if the upper limit exceeds 20 parts by weight, the strength and surface properties may be impaired.

  In the flame-retardant polyester resin composition of the present invention, the initial combustibility is preferably V-0 to V-2 based on UL94 in a molded product having a thickness of 3.2 mm, a length of 127 mm, and a width of 12.7 mm. V-0 is more preferable. Furthermore, in the applications described below, even when used in an environment exposed to heat for a long period of time, maintenance of the combustibility of the molded product and maintenance of the surface appearance are particularly emphasized, so even after a long-term heat aging test. It is preferable that flame retardancy is maintained. That is, it is preferable that the combustibility after the heat treatment at 190 ° C. for 500 hours is the same (maintained) as the initial combustibility.

In addition, the flame-retardant conductive thermoplastic resin composition of the present invention can be obtained after heat treatment for an initial surface resistance (R _i ) when a molded body obtained by an injection molding method is heat-treated at 190 ° C. for 100 hours. The surface resistance value (R ₁₀₀ ) is preferably 100 times or less, more preferably 10 times or less, and particularly preferably 5 times or less.

  The flame retardant conductive thermoplastic resin composition of the present invention can retain excellent flame retardancy and conductivity even when exposed to a high temperature environment for a long time, because of the specific structure that is the component (B) of the present invention. Due to the presence of the conductive carbon compound that is the component (C) of the present invention, the phosphorus-based flame retardant becomes difficult to move even in a high-temperature environment and does not bleed to the surface of the molded body, and therefore flame retardancy is maintained. It is thought that it is from. Since the surface of the molded body does not bleed, the effect of the carbon compound used for imparting surface conductivity is not impaired. Therefore, the effect cannot be achieved even if both the component (B) and the component (C) of the present invention are lacking, and is a feature that is exhibited only when the components (B) and (C) are used in combination. However, it is not easily conceivable even if it is a peer.

  If necessary, additives such as nitrogen compounds, glass fibers, inorganic fillers, pigments, heat stabilizers, lubricants and the like can be added to the flame retardant conductive thermoplastic resin composition of the present invention.

  Examples of the nitrogen compounds include melamine / cyanuric acid adducts, triazine compounds such as melamine and cyanuric acid, and tetrazole compounds. Alternatively, melam and / or melem, which is a dimer and / or trimer of melamine, can be mentioned. Among these, melamine / cyanuric acid adduct is preferable from the viewpoint of mechanical strength.

  In the present invention, the melamine / cyanuric acid adduct is melamine (2,4,6-triamino-1,3,5-triazine) and cyanuric acid (2,4,6-trihydroxy-1,3,5-triazine). ) And / or its tautomers.

  The melamine-cyanuric acid adduct can be obtained by a method of forming a salt by mixing a solution of melamine and a solution of cyanuric acid, a method of forming a salt while adding the other to one solution and dissolving it. The mixing ratio of melamine and cyanuric acid is not particularly limited, but the adduct obtained is preferably close to equimolar, particularly preferably equimolar, from the viewpoint that the resulting adduct is less likely to impair the thermal stability of the thermoplastic polyester resin. .

  The average particle size of the melamine / cyanuric acid adduct in the present invention is not particularly limited, but is preferably 0.01 to 250 μm, and preferably 0.5 to 200 μm from the viewpoint of not impairing the strength properties and molding processability of the resulting composition. Is particularly preferred.

  The nitrogen compound content in the flame-retardant polyester resin composition of the present invention is preferably 10 parts by weight, more preferably 20 parts by weight, and 30 parts by weight as a lower limit value with respect to 100 parts by weight of the thermoplastic resin. Further preferred. If the lower limit of the nitrogen compound content is less than 10 parts by weight, flame retardancy and tracking resistance tend to be reduced. As an upper limit of nitrogen compound content, 100 weight part is preferable and 80 weight part is more preferable. When the upper limit value of the nitrogen compound content exceeds 100 parts by weight, the extrusion processability tends to deteriorate, or the strength, mechanical strength and heat-and-moisture resistance of the welded portion tend to decrease.

  As the glass fiber, a known glass fiber that is generally used can be used, but chopped strand glass fiber treated with a sizing agent is preferably used from the viewpoint of workability.

  In order to improve the adhesion between the resin and the glass fiber, the glass fiber used in the present invention is preferably a glass fiber whose surface is treated with a coupling agent, and may be one using a binder. As the coupling agent, for example, alkoxysilane compounds such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane are preferably used, and as the binder, for example, epoxy resin, urethane resin, etc. Although used preferably, it is not limited to these.

  The said glass fiber may be used independently and may use 2 or more types together. The fiber diameter of the glass fiber is preferably 1 to 20 μm, and the fiber length is preferably 0.01 to 50 mm. When the fiber diameter is less than 1 μm, there is a tendency that a reinforcing effect as expected even if added is not obtained, and when the fiber diameter exceeds 20 μm, the surface property and fluidity of the molded product tend to be lowered. Further, if the fiber length is less than 0.01 mm, there is a tendency that the resin reinforcing effect as expected even if added is not obtained, and if the fiber length exceeds 50 mm, the surface property and fluidity of the molded product are deteriorated. Tend to.

  In the present invention, when the glass fiber content is 100 parts by weight of the thermoplastic resin, the lower limit is preferably 5 parts by weight, more preferably 10 parts by weight, and even more preferably 15 parts by weight. If the content is less than 5 parts by weight, sufficient mechanical strength and heat resistance tend not to be obtained. The upper limit is preferably 100 parts by weight, more preferably 90 parts by weight, and even more preferably 80 parts by weight. If it exceeds 100 parts by weight, the surface properties and extrusion processability of the molded product tend to be lowered.

  The inorganic filler used in the present invention is not particularly limited as long as it is a fibrous and / or granular inorganic filler, but by adding the inorganic filler, the strength, rigidity, heat resistance, etc. are greatly improved. Can be made.

  Specific examples of the inorganic filler used in the present invention include, for example, metal fibers, aramid fibers, asbestos, potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, mica, clay, calcium carbonate, sulfuric acid. Of these, barium, titanium oxide, aluminum oxide, and the like. Among these, in order to obtain excellent electrical characteristics, particularly excellent tracking resistance, it is preferable to use a particulate filler, particularly talc.

  The content of the inorganic filler in the present invention is preferably 1 part by weight, more preferably 3 parts by weight, and still more preferably 5 parts by weight when the thermoplastic resin is 100 parts by weight. When the content of the inorganic filler is less than 1 part by weight, there is a tendency that improvement effects such as electrical characteristics and rigidity are difficult to obtain. The upper limit is preferably 60 parts by weight, more preferably 40 parts by weight, and even more preferably 20 parts by weight. If the content of the inorganic filler exceeds 60 parts by weight, the surface properties, mechanical properties, extrusion processability, and fluidity at the time of moldability may be deteriorated.

  Examples of the heat stabilizer include bisphenol A diglycidyl ether, butyl glycidyl ether, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and tris (2,4-di-t. -Butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate]. 0.1-3.0 weight part is preferable with respect to 100 weight part of thermoplastic resins, and, as for the compounding quantity of a heat stabilizer, 0.5-1.5 is more preferable. If the blending amount of the heat stabilizer is less than 0.1 parts by weight, mechanical properties due to thermal deterioration during processing may be deteriorated. If it exceeds 3.0 parts by weight, gas generation or gold may be generated during molding. Mold contamination may occur.

  Examples of the pigment include commercially available pigments such as titanium oxide, and examples of the lubricant include polycondensates such as ethylenediamine, stearic acid, and sebacic acid, and esters such as montanic acid.

  The method for producing the flame retardant conductive thermoplastic resin composition of the present invention is not particularly limited. For example, the thermoplastic resin (A), the organic phosphorus flame retardant (B), the conductive carbon compound (C). These can be melt-kneaded using various common kneaders. Examples of the kneader include a single screw extruder and a twin screw extruder, and a twin screw extruder with high kneading efficiency is particularly preferable.

  The flame-retardant conductive thermoplastic resin composition obtained in the present invention has high flammability and conductivity, and even when used in a high-temperature environment, the flame-out of the flame retardant on the surface of the molded product is suppressed. Since the initial characteristics are maintained, it is suitably used for electrical and electronic parts such as home appliances and OA equipment, housings, etc. that require long-term reliability.

  Next, the composition of the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

  The resins and raw materials used in the examples and comparative examples are shown below.

Thermoplastic resin (A)
Polyester resin: logarithmic viscosity (measured at 25 ° C. in a mixed solvent in which phenol / tetrachloroethane is 1/1 in weight ratio, the same applies hereinafter) 0.65 dl / g of polyethylene terephthalate (PET; manufactured by Kanebo Gosei Co., Ltd.) EFG-70) dried at 140 ° C. for 3 hours.
Polycarbonate resin: Teflon A2200 manufactured by Idemitsu Chemical Co., Ltd.
Polyamide resin: Unitika Nylon A1030BRL manufactured by Unitika Ltd.
Polyphenylene ether resin: Iupiace AH90 manufactured by Mitsubishi Engineering
-Polypropylene resin: Noblen AZ864, manufactured by Sumitomo Chemical Co., Ltd.

Organophosphorous flame retardant (B)
・ Producted in Production Example 1

Conductive carbon compound (C)
・ Ketjen Black (registered trademark) manufactured by Ketjen Black International Co., Ltd., master batch pellet in which fibrillar carbon compound is dispersed at a concentration of 20% in PA6, trade name MB4020-00 (manufactured by Hyperion Catalysis International Inc.) did.

Stabilizer, bisphenol A diglycidyl ether, butyl glycidyl ether (Asahi Denka Kogyo Co., Ltd., EP-22)
Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (Asahi Denka Kogyo Co., Ltd., ADK STAB PEP-36)
Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, IRGANOX 1010)

Production Example 1
In a vertical polymerization machine having a distillation tube, a rectification tube, a nitrogen introduction tube and a stirrer, the following general formula (3):

60 parts by weight of itaconic acid in an equimolar amount with respect to 100 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide represented by 160 parts by weight was added, and gradually heated to 120 to 200 ° C. in a nitrogen gas atmosphere, and stirred for about 10 hours to obtain a phosphorus-based flame retardant solution. To the obtained phosphoric flame retardant solution, 0.1 part by weight of antimony trioxide and 0.1 part by weight of zinc acetate were added, and further under a vacuum reduced pressure of 1 Torr (= 1.33 × 10 ² Pa) or less. While maintaining the temperature at 220 ° C., a polycondensation reaction was carried out while distilling ethylene glycol. About 5 hours later, the distillation amount of ethylene glycol was extremely reduced, and thus the reaction was considered to be completed. The obtained organic phosphorus flame retardant (B) was a solid having a molecular weight of 7000, and the phosphorus content was 8.3%.

  In addition, the evaluation method in this specification is as showing below.

<Flame retardance>
Based on the UL94 standard V-0 test, the initial flammability and the flammability after treatment at 190 ° C. for 500 hours were evaluated using the obtained bar-shaped test piece having a thickness of 3.2 mm.

<Conductivity>
A resistance value measuring device R8340A manufactured by Advantest Corporation was used. The test piece was measured after conditioning for 24 hours at 25 ° C. and 50% RH on a 120 mm × 120 mm thick 3 mm flat plate molded product.

Examples 1 to 6, 8, and 9 and Reference Example 7
The raw materials (A) to (C) were dry blended in advance according to the composition (unit: parts by weight) shown in Table 1. Using a vent type 44 mmφ same direction twin screw extruder (manufactured by Nippon Steel Works, TEX44), the mixture was supplied from the hopper hole and melt kneaded at a cylinder set temperature of 250 to 280 ° C. to obtain pellets. .

  After drying the obtained pellets at 140 ° C. for 3 hours, injection molding is performed using an injection molding machine (clamping pressure: 80 tons) under conditions of a cylinder temperature of 280 ° C. to 250 ° C. and a mold temperature of 90 ° C. A disk-shaped molded body having a diameter of 100 mmφ × a thickness of 1.6 mm and a bar molded body having a diameter of 127 mm × 12.7 mm × thickness of 3.2 mm were obtained. Using the obtained test piece, warpage evaluation and flammability evaluation were performed according to the above criteria.

The evaluation results in Examples 1 to 6, 8 and 9 and Reference Example 7 are shown in Table 1.

Comparative Examples 1-8
The raw materials (A) to (C) were pelletized and injection-molded in the same manner as in the examples according to the composition (unit: parts by weight) shown in Table 2, to obtain test pieces, and the same evaluation method The experiment was conducted.

  The evaluation results in Comparative Examples 1 to 8 are shown in Table 2.

  Comparing the results of Examples and Comparative Examples, the flame retardant conductive thermoplastic resin composition of the present invention is obtained by adding an organophosphorus flame retardant (B) conductive carbon compound (C) to the thermoplastic polyester resin (A). It turns out that it is excellent in the bleed-out suppression of a flame retardant by mix | blending.

  The flame-retardant conductive thermoplastic resin composition obtained in the present invention has high flammability and conductivity, and can maintain its initial characteristics even when the molded body is exposed to a high temperature environment. In particular, it is suitably used for electrical and electronic parts such as home appliances and OA equipment, housings, etc., which are complex in shape and exposed to high temperature environments.

Claims (4)

With respect to 100 parts by weight of the thermoplastic resin (A), the following general formula (1):

A flame retardant conductive thermoplastic resin composition containing 10 to 80 parts by weight of an organic phosphorus flame retardant (B) and 0.1 to 20 parts by weight of a conductive carbon compound (C) represented by: A flame retardant conductive thermoplastic resin composition in which the conductive carbon compound (C) is granular Ketjen Black (registered trademark) . The flame retardant conductive thermoplastic resin composition according to claim 1, wherein the following conditions (a) and (b) are satisfied.
(A) In a molded product having a thickness of 3.2 mm, a length of 127 mm, and a width of 12.7 mm, the initial flammability is V-0 to V-2 based on UL94, and combustion after heat treatment at 190 ° C. for 500 hours The property is the same as the initial combustibility.
(B) The ratio (R ₁₀₀ / R _i ) of the value (R ₁₀₀ ) after 190 hours at 190 ° C. to the initial value (R _i ) of the surface specific resistance value is 100 or less. The flame-retardant conductive thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin (A) is at least one selected from polyester resins, polycarbonate resins, polyamide resins, polyphenylene ether resins, and polyolefin resins. The resin molding containing the flame-retardant conductive thermoplastic resin composition in any one of Claims 1-3 .