JP6423140B2 - Non-halogen flame retardant resin composition and molded article - Google Patents

Description

  The present invention relates to a non-halogen flame retardant resin composition and a molded body.

  Thermoplastic polyurethane (hereinafter sometimes referred to as “TPU”) has excellent mechanical properties, high rebound resilience, and excellent moldability such as injection molding and extrusion molding. Automotive parts, synthetic leather, wire coating Used in various fields such as tubes. However, thermoplastic polyurethane has poor flame retardancy, and its use has been difficult in applications where high flame retardancy is required. In order to solve this problem, various techniques for imparting flame retardancy to resin compositions containing thermoplastic polyurethane have been developed.

  For example, addition of a flame retardant containing a halogen-based element such as bromine can be mentioned. However, the use of halogen-based flame retardants can provide high flame resistance, but on the other hand, there are concerns about the corrosive gas generated during processing and the burden on the environment. In recent years, high flame resistance has been achieved without using halogen-based elements. There is a demand for imparting sex.

  Therefore, high flame retardancy is achieved by blending thermoplastic polyurethane with flame retardants that do not contain halogen elements such as organic phosphates and melamine derivatives (halogen-free flame retardants) and talc and dipentaerythritol at a specific ratio. It is known that, for example, in the UL-94 vertical combustion test (underwriters laboratory), “V-0” level and melt dripping (drip) during combustion can be suppressed (Patent Document 1). However, the composition obtained by this method has many essential components for exhibiting high flame retardancy, and it is difficult to design a material suitable for various applications, so that it exhibits excellent flame retardancy with fewer components. It is demanded. Furthermore, although talc is a highly safe material, since it is a natural mineral, it may rarely contain a trace amount of impurities such as asbestos, and there are concerns about safety (Non-patent Document 1). ). For this reason, in the manufacturing site etc. which handle talc as a manufacturing raw material, since high level safety ensuring is calculated | required, it is calculated | required to provide high flame retardance, without making talc an essential component.

Special table 2011-508024 gazette

Ministry of Health, Labor and Welfare, Labor Standards Bureau, Department of Health and Safety, Chemical Substances Management Section Yoshio Hirano, Ministry of Health, Labor and Welfare [online], October 16, 2006 [Search August 30, 2012], Internet URL: http: //www.mhlw .go.jp / houdou / 2006/10 / h1016-3.html

  Therefore, the problem to be solved by the present invention is that a resin composition containing thermoplastic polyurethane does not contain halogen-based elements and talc as essential components, and is a less essential component, which is a molten dripping (drip) during combustion. It is providing the flame-retardant resin composition which has the outstanding flame retardance, and its molded object.

  As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by blending a specific amount and a specific ratio of an organic phosphate and a melamine derivative in flame retardant polyurethane. The present invention has been found to solve the present invention.

That is, the present invention
A non-halogen flame retardant resin composition containing (a) a thermoplastic polyurethane, (b) an organic phosphate and (c) a melamine derivative as essential components, the composition comprising: (a) a thermoplastic polyurethane Is in the range of 55 to 70% by mass, (b) the organic phosphate is in the range of 18 to 30% by mass, (c) the melamine derivative is in the range of 10 to 30% by mass, and the mass ratio The present invention relates to a non-halogen flame-retardant resin composition characterized by being in a range of (b) / (c) = 1/1 to 2/1, and a molded product thereof.

  According to the present invention, in a resin composition containing a thermoplastic polyurethane, an excellent difficulty that does not contain a halogen-based element and talc as essential components, is a less essential component, and does not melt and drip during combustion. A flame-retardant resin composition having flame retardancy and a molded product thereof can be provided.

  The non-halogen flame retardant resin composition of the present invention is a non-halogen flame retardant resin composition containing (a) a thermoplastic polyurethane, (b) an organic phosphate and (c) a melamine derivative as essential components. In the composition, (a) the thermoplastic polyurethane is in the range of 55 to 70% by mass, (b) the organic phosphate is in the range of 18 to 30% by mass, and (c) the melamine derivative is in the range of 10%. It is the range of -30 mass%, and is the range of (b) / (C) = 1/1-2/1 by mass ratio.

  As the (a) thermoplastic polyurethane used in the present invention, any known and conventional ones can be used, but they were obtained by synthesizing from an organic diisocyanate (a1), a chain extender (a2) and a polymer polyol (a3). It is preferable to use those, and more specifically, organic diisocyanate (a1) selected from the group consisting of aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates, chain extenders (a2) and polymer polyols (a3) More preferably, the high molecular weight polyol (a3) is obtained by synthesizing a polyether polyol and / or a polycarbonate polyol having a number average molecular weight of 500 to 30,000 as raw materials.

  Examples of the organic diisocyanate (a1) as a constituent component include methylene diisocyanate, ethylene diisocyanate, 1-methylethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1,4-diisocyanate, hexamethylene diisocyanate, octamethylene. Aliphatic diisocyanates such as diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, alicyclic diisocyanates such as P, P'-cyclohexylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'- Such as diphenylmethane diisocyanate, P-phenylene diisocyanate, tolylene diisocyanate, 1,5-naphthylene diisocyanate And aromatic diisocyanates are. These isocyanates can be used alone or in combination of two or more.

  Examples of the low molecular weight diol (a2i) having 2 to 10 carbon atoms used as the chain extender (a2) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1, Aliphatic glycols such as 4-butanediol, 2-methylpentanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, octanediol, nonanediol, decanediol, trimethylolpropane, glycerin, Examples thereof include low-molecular alicyclic diols such as cyclohexanediol and cyclohexanemethanol, and aromatic glycols such as bishydroxyethoxybenzene and xylene glycol. These polyols (a2i) can be used alone or in combination of two or more. The number of average functional groups of these polyols (a2i) alone or in mixture is preferably 2 or more, and the average molecular weight is preferably in the range of 50 to 400. When rubber elasticity is required for the molded article to be obtained, it is preferable to use an aliphatic diol as the polyol (a2i).

  Examples of the polymer polyol (a3) include polycarbonate polyol, polyester polyol, and polyether polyol. These polyols can be used alone or in combination of two or more. The average functional group number of these polymer polyols (a3) alone or in mixture is preferably 2 or more, and the average molecular weight is preferably in the range of 500-30000. The average number of functional groups is preferably about 2, the average molecular weight is particularly preferably in the range of 500 to 5000, and the average molecular weight is most preferably in the range of 500 to 3000.

  In addition, as the polymer polyol (a3), it is particularly preferable to use a polycarbonate polyol in view of excellent weather resistance and heat resistance of the obtained thermoplastic polyurethane resin. The polycarbonate polyol can be easily produced, for example, by subjecting a low molecular polyol and a dialkyl carbonate or diaryl carbonate to a condensation reaction. Examples of the low molecular polyol include 1,6-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and cyclohexanedimethanol. Examples of the dialkyl carbonate or diaryl carbonate include diphenyl carbonate, dimethyl carbonate, diethyl carbonate, and ethylene carbonate.

  Examples of the polycarbonate polyol include a lactone-modified polycarbonate polyol obtained by ring-opening addition polymerization of a lactone and a polycarbonate polyol co-condensed with another polyester polyol or polyether polyol and the like. A condensed polycarbonate polyol is mentioned.

  Examples of the polyester polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,6-pentanediol, and cyclohexane. One or more of dimethanol or other low molecular diol components and one or more low molecular dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, or A lactone polyol obtained by polycondensation with two or more or ring-opening polymerization of a lactone, such as polypropiolactone polyol, polycaprolactone polyol, polyparerolactone polyol, and the like, is not limited thereto. Absent.

  Examples of the polyether polyol include polypropylene ether polyol, polytetramethylene ether polyol, hexamethylene ether polyol, and the like.

The production of the thermoplastic polyurethane resin (a) of the present invention can be carried out by production of an ordinary thermoplastic polyurethane. For example, a two-component solution of a prepolymer of a terminal isocyanate and a chain extender (a2) in which an excess isocyanate (a1) is preliminarily reacted with the polymer polyol (a3) at a temperature of 120 ° C. or lower, preferably 100 ° C. or lower. (Prepolymer method), or a method in which two liquids (one-shot method) of a polyol compound and an isocyanate (a1) mixed with a polymer polyol (a3) and a chain extender (a2) are weighed, mixed and stirred, A method in which the raw material of the above is weighed with a metering pump, vigorously mixed and stirred, then poured onto a vat, further reacted in a temperature range of 80 to 200 ° C., preferably 120 to 180 ° C., and then pulverized. Can be manufactured.
Further, for example, the above raw materials are supplied to an extruder set in the range of 80 to 250 ° C., preferably in the range of 120 to 250 ° C., and polymerization is performed while kneading and conveying the raw materials in the extruder. Can also be manufactured by extruding from the die.

  In the production method of the present invention, the reaction equivalent ratio of isocyanate group and active hydrogen is not particularly limited, but is usually 0.95 to 1.05, preferably 0.96 to 1.04.

  A catalyst need not be used, but can be used. As the catalyst, any of the commonly used urethanization catalysts can be used. For example, bismuth, lead, tin, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, Examples include organic compounds such as vanadium, copper, manganese, zirconium, and calcium, and inorganic compounds. Preferred catalysts are organometallic compounds, particularly dialkyl tin compounds. Examples of typical organic tin catalysts include stannous octoate, stannous oleate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin malate, dibutyltin mercaptopropionate, and dibutyltin dodecylmercapto. . The amount of the catalyst to be used is not particularly limited because it is determined by the properties of other raw materials, reaction conditions, desired reaction time, etc., but the catalyst is generally 0.0001 to 5 of the total weight of the reaction mixture. It is used by mixing on the active hydrogen compound side in the range of mass%, preferably 0.0001 to 2 mass%.

  The (a) thermoplastic polyurethane resin of the present invention preferably has a flow start temperature of 125 ° C. or higher in terms of excellent heat resistance.

  The weight average molecular weight of the thermoplastic polyurethane resin used in the present invention is in the range of 100,000 to 700,000, preferably in the range of 100,000 to 300,000. In addition, said mass average molecular weight is an average molecular weight measured using GPC (gel filtration chromatography).

  As the (b) organophosphate used in the present invention, any of the known and conventional ones can be used. However, a polyphosphazene compound obtained by ring-opening polymerization of a metal phosphinate, an ammonium phosphate compound, and cyclophosphazene. It is preferable that it is at least one selected from the group consisting of: phosphinic acid metal salts are more preferred because of their excellent char (carbonized layer) -forming properties during combustion and high decomposition temperatures.

  As the phosphinic acid metal salt, the following general formula (1) or (2)

（式中、Ｒ^１、Ｒ^２は、それぞれ、炭素数１〜６のアルキル基または炭素数１２以下のアリール基であり、Ｒ^３は炭素原子数１〜１０の直鎖もしくは分岐鎖状アルキレン基、炭素原子数６〜１０のアリーレン基、炭素原子数６〜１０のアルキルアリーレン基または炭素原子数６〜１０のアリールアルキレン基であり、Ｍは、カルシウム、アルミニウム又は亜鉛であり、ｍ＝２または３、ｎ＝１、２または３、ｘ＝１または２である。）で表されるホスフィン酸金属塩が挙げられる。

Wherein R ¹ and R ² are each an alkyl group having 1 to 6 carbon atoms or an aryl group having 12 or less carbon atoms, and R ³ is a linear or branched alkylene group having 1 to 10 carbon atoms. , An arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms, M is calcium, aluminum, or zinc, and m = 2 or 3, n = 1, 2, or 3, and x = 1 or 2.).

  As phosphinic acid metal salts, aluminum salts of organic phosphinic acids such as EXOLIT OP1230, EXOLIT OP1240, EXOLIT OP930, EXOLIT OP935, etc. of Clariant Japan KK, or blends of aluminum phosphinic acid such as EXOLIT OP1312 and melamine polyphosphate Can be used.

  Examples of ammonium phosphate compounds that can be used include ammonium polyphosphate, polyphosphate amide, ammonium polyphosphate amide, and carbamic acid polyphosphate.

  As a polyphosphazene compound obtained by ring-opening polymerization of cyclophosphazene, SPR-100, SA-100, SR-100, SRS-100, SPB-100L, etc. manufactured by Otsuka Chemical Co., Ltd. can be used.

  As the (c) melamine derivative used in the present invention, any known and commonly used melamine derivatives can be used, but 1 selected from the group consisting of melamine cyanurate, melamine, dimelamine sulfate, melamine phosphate, melamine polyphosphate and melamine pyrophosphate. It is preferable to use at least one species, and among them, melamine cyanurate and melamine cyanurate are particularly preferable for ether polyurethanes and melamine cyanurates and carbonate polyurethanes, respectively, because they are excellent in flame retardant properties. As melamine cyanurate, MC-6000 manufactured by Nissan Chemical Industries, Ltd. can be used. Furthermore, as the melamine phosphate compound, melamine polyphosphate such as MELAPUR200 of BASF Japan Ltd., SUN SHINE COMMERCIAL & INDUSTRIAL CORP. Melamine pyrophosphate such as MPP-1 from the company, melamine phosphate, melamine orthophosphate, etc. can be used.

The non-halogen flame retardant resin composition of the present invention comprises (a) a thermoplastic polyurethane, (b) an organic phosphate, and (c) 55 to 55 mass% of (a) the thermoplastic polyurethane. In the range of 70% by mass, preferably in the range of 60-68% by mass, (b) the organophosphate is in the range of 18-30% by mass, preferably in the range of 18-25% by mass, and (c) melamine The derivative is in the range of 10 to 30% by mass, preferably in the range of 15 to 25% by mass.
Moreover, (b) organophosphate and (c) melamine derivative are the range of (b) / (c) = 1/1-2/1 by mass ratio.

  When (a) thermoplastic polyurethane is 55% by mass or more, kneading with (b) organophosphate and (c) melamine derivative is easy and excellent in mechanical strength. % Or less is preferable because the content of the organic phosphate or melamine derivative, which exhibits a relatively flame-retardant effect, is high, and thus the flame retardancy is excellent. Further, if (b) the organic phosphate and (c) the melamine derivative are within the above ranges, the resin properties of the thermoplastic polyurethane are maintained and the flame retardancy is excellent. This is preferable because dripping of the liquid can be suppressed.

  In addition to the above components (a) to (c), the non-halogen flame retardant resin composition of the present invention may further include a metal hydrate such as magnesium hydroxide, calcium carbonate, silica, red phosphorus, etc. Inorganic compounds, antioxidants such as phenols, thioethers, phosphites, lactones, vitamins, UV absorbers such as benzotriazoles, benzophenones, benzoates, triazines, hindered amines, metal inertness Stabilizers such as agents, release agents and lubricants such as silicones and fatty acid amides, dispersants such as metal soaps and fatty acid amides, colorants and foaming agents such as dyes and organic and inorganic pigments, p-toluene It is also possible to add plasticizers such as sulfonamides, benzoate plasticizers, and polyester plasticizers. The types and amounts of these additives By adjusting, the target function can be freely adjusted. It is also possible to improve the tackiness (stickiness) of thermoplastic polyurethane by adding spherical particles in the range of 1 to 50 μm made of organic and inorganic materials such as acrylic beads, urethane beads and glass beads.

  The non-halogen flame-retardant resin composition of the present invention is a mixture of the above-mentioned components in a predetermined amount, a single screw extrusion kneader, an open roll mixer, a pressure kneader, a Banbury mixer, a twin screw extrusion kneading. Using a known mixer such as a machine, the resin is set at a melting point or higher and melt kneaded. Among these, the twin screw extrusion type kneader is preferable in terms of kneading properties and productivity. After the melt-kneading, the pellets of the flame retardant resin composition obtained by pulverization as desired are further subjected to a molding machine, and known as extrusion molding, injection molding, compression molding, blow molding, injection compression molding, etc. The flame-retardant resin molding is produced by applying to various molding methods.

  The non-halogen flame-retardant resin composition of the present invention is extremely excellent in flame retardancy, does not generate halogen gas during combustion and incineration, and is melt-dropped when it contains thermoplastic polyurethane. Generation of (drip) can be eliminated, and it can be used in applications where high flame retardancy is required. For this reason, the non-halogen flame-retardant resin composition of the present invention can be applied to electronic parts molding materials, etc., such as films and general household wallpaper. Can be suitably used for applications such as a wire coating material, a sheet, and a tube.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these specific examples. In Examples and Comparative Examples, unless otherwise specified,% display and part display are based on mass.
(Examples 1-6, Comparative Examples 1-3)
After mixing with the components and blending ratios described in Tables 1 to 3, the mixture was melt-kneaded with a 30 mmφ biaxial vent type extruder (set temperature: 150 to 200 ° C.), and pelletized. The pellet was press-molded (set temperature: 150 to 200 ° C.) to prepare a test piece having a length of 127 mm × width of 12.7 mm × thickness of 3 mm. Evaluation of each characteristic was implemented with the following method, and the evaluation result was combined with Tables 1-3, and was described.
(Flame retardancy test and determination of presence or absence of drips)
It measured based on UL-94 vertical combustion test using the test piece produced in Examples 1-6 and Comparative Examples 1-3. Moreover, the presence or absence of melt dripping (drip) at the time of measurement was evaluated according to the following criteria.
With drips: With No drips: Without

In the table, each component is as follows.
TPU1: Ether type polyurethane “PANDEX T-8180N” DCI Bayer Polymer Co., Ltd. TPU2: Ester type polyurethane (carbonate type) “PANDEX T-9280N” DIC Bayer Polymer Co., Ltd. Organic phosphate: diethyl phosphate aluminum salt “Exolit OP-930 "Clariant Japan Co., Ltd. Melamine Derivatives 1: Melamine Cyanurate" MC-6000 "Nissan Chemical Industries, Ltd. Melamine Derivatives 2: Melamine Polyphosphate" Melapur200 "BASF Japan Ltd. Melamine Derivatives 3: Melamine pyrophosphate" MPP-1 ""SUN SHINE COMMERCIAL & INDUSTRIAL CORP

Claims (6)

A non-halogen flame-retardant resin composition obtained by melt-kneading a mixture containing (a) a thermoplastic polyurethane, (b) an organic phosphate and (c) a melamine derivative as essential components,
The (c) melamine derivative is at least one selected from the group consisting of melamine cyanurate, melamine, dimelamine sulfate, melamine phosphate, melamine polyphosphate and melamine pyrophosphate,
The composition comprises (a) thermoplastic polyurethane, (b) organophosphate, and (c) thermoplastic polyurethane in a range of 55 to 70% by mass, b) The organic phosphate is in the range of 18 to 30% by mass, (c) the melamine derivative is in the range of 10 to 30% by mass, and (b) / (c) = 1/1 to 1 in mass ratio. 2/1 non-halogen flame retardant resin composition (however, containing talc, and
A flame retardant polymer composition comprising:
a) one or more thermoplastic elastomers;
b) 18 or about 18-50 or about 50 weight percent, based on the total weight of the flame retardant polymer composition;
b1) at least one difficulty comprising a material selected from the group consisting of phosphinates of formula (I); diphosphinates of formula (II); polymers of (I); polymers of (II); and mixtures of two or more thereof Flame retardant

Wherein R ₁ and R ₂ are independently selected from hydrogen, linear or branched C ₁ -C ₆ alkyl groups, and aryl groups; R ₃ is linear or branched C ₁ -C ₁₀ alkylene group, C ₆ -C ₁₀ arylene group, an alkyl arylene group or an arylalkylene group; M is selected calcium, magnesium, aluminum, from the group consisting of zinc and mixtures thereof; m is 2-3; n is 1 or 3; x is 1 or 2);
b2) a phosphorus-containing amino composition selected from the group consisting of melamine phosphate, melamine phosphate derivatives and mixtures thereof, reaction products of ammonia and phosphoric acid, polyphosphates of said reaction products, and mixtures thereof;
b3) Zeolite
A flame retardant mixture comprising
i) b1) is present in the flame retardant polymer composition in an amount of 15 weight percent or more based on the total weight of the flame retardant polymer composition, and ii) b2) is present in the amount of b2) present in the flame retardant mixture in an amount less than the amount of b1)
With flame retardant mixture
Flame retardant polymer composition comprising
except for. ) A non-halogen flame-retardant resin composition obtained by melt-kneading a mixture containing (a) a thermoplastic polyurethane, (b) an organic phosphate and (c) a melamine derivative as essential components,
The (b) organophosphate is represented by the following general formula (1) or (2)

Wherein R ¹ and R ² are each an alkyl group having 1 to 6 carbon atoms or an aryl group having 12 or less carbon atoms , and R ³ is a linear or branched alkylene group having 1 to 10 carbon atoms. , An arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms, M is calcium, aluminum, or zinc, and m = 2 or 3, n = 1, 2, or 3, x = 1 or 2.)
The composition comprises (a) thermoplastic polyurethane, (b) organophosphate, and (c) thermoplastic polyurethane in a range of 55 to 70% by mass, b) The organic phosphate is in the range of 18 to 30% by mass, (c) the melamine derivative is in the range of 10 to 30% by mass, and (b) / (c) = 1/1 to 1 in mass ratio. 2/1 non-halogen flame retardant resin composition (however, containing talc, and
A flame retardant polymer composition comprising:
a) one or more thermoplastic elastomers;
b) 18 or about 18-50 or about 50 weight percent, based on the total weight of the flame retardant polymer composition;
b1) at least one difficulty comprising a material selected from the group consisting of phosphinates of formula (I); diphosphinates of formula (II); polymers of (I); polymers of (II); and mixtures of two or more thereof Flame retardant

Wherein R ₁ and R ₂ are independently selected from hydrogen, linear or branched C ₁ -C ₆ alkyl groups, and aryl groups; R ₃ is linear or branched C ₁ -C ₁₀ alkylene group, C ₆ -C ₁₀ arylene group, an alkyl arylene group or an arylalkylene group; M is selected calcium, magnesium, aluminum, from the group consisting of zinc and mixtures thereof; m is 2-3; n is 1 or 3; x is 1 or 2);
b2) a phosphorus-containing amino composition selected from the group consisting of melamine phosphate, melamine phosphate derivatives and mixtures thereof, reaction products of ammonia and phosphoric acid, polyphosphates of said reaction products, and mixtures thereof;
b3) Zeolite
A flame retardant mixture comprising
i) b1) is present in the flame retardant polymer composition in an amount of 15 weight percent or more based on the total weight of the flame retardant polymer composition, and ii) b2) is present in the amount of b2) present in the flame retardant mixture in an amount less than the amount of b1)
With flame retardant mixture
Flame retardant polymer composition comprising
except for. ) The non-halogen flame retardant according to claim 2, wherein the (c) melamine derivative is at least one selected from the group consisting of melamine cyanurate, melamine, dimelamine sulfate, melamine phosphate, melamine polyphosphate and melamine pyrophosphate. Resin composition.   Any one of Claims 1-3 whose (c) melamine derivative is 15-30 mass% with respect to the total mass of (a) thermoplastic polyurethane, (b) organophosphate, and (c) melamine derivative. Non-halogen flame retardant resin composition described in 1.   The thermoplastic polyurethane resin (a) is obtained by synthesizing from an organic diisocyanate (a1), a chain extender (a2), and a polymer polyol (a3). Non-halogen flame retardant resin composition.   The molded object formed by shape | molding the non-halogen-type flame-retardant resin composition as described in any one of Claims 1-5.