JP6497774B2 - Thermosetting composition for flame retardant polyurethane resin, flame retardant polyurethane resin and flame retardant article, and battery pack - Google Patents

Description

  The present invention relates to a thermosetting composition for a flame-retardant polyurethane resin, a flame-retardant polyurethane resin obtained by thermosetting the composition, a flame-retardant article comprising the polyurethane resin, and a battery pack comprising the article. .

  2. Description of the Related Art Conventionally, thermoplastic resins such as polyester are mainly used as outer members such as casings of electronic and electric devices, component packages, and battery packs. Further, in order to realize a reduction in size and weight of the product, it is preferable that such a thermoplastic resin can be used in a thin shape.

  However, since such a thermoplastic resin generally has a high curing (molding) temperature, it cannot often be integrally molded with a heat-sensitive component or battery. Further, since the curing is fast and the fluidity in the mold is also poor, it is considered that defects due to coating defects and remaining bubbles are likely to occur in the thin part of the molded product.

  In addition, when the product requires flame retardancy, it is necessary to use a flame retardant. Conventionally, halogen compounds such as chlorine and bromine have been used as flame retardants, but they tend to be avoided because they have a large impact on the global environment, such as being a source of dioxins.

  In view of the above, in this field, as a material having a relatively low curing temperature and excellent fluidity even in a mold, a thermosetting composition comprising various polyols and polyisocyanates containing a non-halogen flame retardant is used. Sometimes. For example, Patent Document 1 discloses a casting composition containing a polyol (liquid polybutadiene polyol), a polyisocyanate, and a phosphate ester compound as a flame retardant.

  However, a polyurethane resin obtained by curing such a conventional casting composition does not have sufficient flame retardancy in a thin state of about several hundred microns. Specifically, in the UL94-VTM (Thin Material Vertical Combustion Test Test), the flammable combustion time is long, and many combustion fallen objects (drip) are generated. For this reason, a large amount of phosphorus-based flame retardant must be used, but it tends to be difficult to achieve both fire resistance in a thin state and physical properties such as impact resistance and deflection resistance.

JP-A-5-112625

  The present invention is a thermosetting composition for a flame-retardant polyurethane resin containing a polyol, a polyisocyanate, and a phosphorus-based flame retardant, and is VTM-2 or higher (VTM-2, VTM-1, or VTM-) in a UL94-VTM test. It is an object of the present invention to provide a thermosetting composition capable of forming a flame retardant polyurethane resin that exhibits a thin flame retardancy of 0) and is excellent in impact resistance and deflection resistance.

  As a result of intensive studies, the inventor of the present invention uses a phosphazene compound as the phosphorus-based flame retardant in a thermosetting composition for a flame-retardant polyurethane resin containing a polyol, a polyisocyanate, and a phosphorus-based flame retardant. It has been found that a composition capable of solving the above-mentioned problems can be obtained by further using fluoroethylene particles as a flame retardant.

  That is, the present invention includes a flame retardant containing a polyol (A), a polyisocyanate (B), a phosphazene compound (C) and calcined polytetrafluoroethylene particles (D), and, if necessary, a urethanization catalyst (E). The present invention relates to a thermosetting composition for polyurethane resin, a flame retardant polyurethane resin obtained by thermosetting the composition, a flame retardant article comprising the flame retardant polyurethane resin, and a battery pack comprising the flame retardant polyurethane resin.

  The thermosetting composition of the present invention has excellent fluidity in the mold and is cured at a relatively low temperature. Moreover, according to this composition, the thin flame retardance more than VTM-2 is shown in a UL94-VTM test. Specifically, even when a polyurethane resin obtained by heat-curing the composition is combusted in a film state according to the same standard, the flameless combustion duration is long, and combustion drops (drip) are generated from the film. It becomes difficult. More particularly, the film shrinks (deforms) when burned. This is considered to be a cause of the difficulty of producing combustion droplets. In addition, a cured product obtained from the polyurethane resin is excellent in impact resistance and hardly bends even when a load is applied. The cured product also has good bending strength and flexural modulus. Therefore, the thermosetting composition of the present invention and the polyurethane resin obtained from the composition are useful as outer members such as casings of electronic and electric devices, package of parts, battery packs and / or as raw materials thereof.

  The thermosetting composition for a flame-retardant polyurethane resin according to the present invention (hereinafter sometimes simply referred to as a thermosetting composition) comprises a polyol (A) (hereinafter referred to as component (A)), a polyisocyanate (hereinafter referred to as component (A)). B) (hereinafter referred to as component (B)), phosphazene compound (C) (hereinafter referred to as component (C)) and polytetrafluoroethylene particles (D) (hereinafter referred to as component (D)) are essential components. And urethanization catalyst (E) (hereinafter referred to as component (E)) as an optional component.

  As the component (A), various known materials can be used without particular limitation as long as they can be used as the polyol component of the flame-retardant polyurethane resin. In the present invention, in particular, the amino group-containing polyol (a1) (hereinafter also referred to as component (a1)), phosphorus-containing diol (a2) (hereinafter referred to as component (a2)), and other polyols (a3) ( Hereinafter, it is preferable to use (a3) component).

  The component (a1) is a polyol having at least one amino group in the molecule, and does not contain a phosphorus atom in a narrow sense. Since the component (a1) has a nitrogen atom in the molecule, the component (a1) itself has self-digestibility and contributes to improvement in thin flame retardancy. It also contributes to impact resistance.

  Examples of the component (a1) include a nitrilotris alkanol (a1-1) represented by the following general formula (1) (hereinafter referred to as the component (a1-1)), and the component (a1-1) as an initiator. And polyether polyol (a1-2) (hereinafter referred to as (a1-2) component) obtained by addition-reacting an alkylene oxide represented by the following general formula (3) to this, and the following general formula (2) From polyether polyol (a1-3) (hereinafter referred to as component (a1-3)) obtained by addition-reacting an alkylene oxide represented by the following general formula (3) with an alkylenediamine represented as an initiator. At least one polyol selected from the group consisting of

(In formula (1), R ¹ represents hydrogen or a methyl group, respectively.)

(In formula (2), R ² represents an alkylene group having 2 to 4 carbon atoms.)

(In formula (3), R ³ represents hydrogen or an alkyl group having 1 to 3 carbon atoms.)

  Examples of the component (a1-1) include 2,2 ′, 2 ″ -nitrilotrisethanol, 1,1 ′, 1 ″ -nitrilotris (1-propanol), 1,1 ′, 1 ″. -Nitrilotris (2-propanol), bis (2-hydroxyisopropyl) ethanol, etc. are mentioned. In addition, this (a1-1) component may be a commercial item, for example, Leocon MA-170 (product made from Lion Corporation), Exenol 480A (product made from Asahi Glass Co., Ltd.), etc. are mentioned.

  As described above, the component (a1-2) is obtained by subjecting the component (a1-1) to an addition reaction with an alkylene oxide represented by the general formula (3). Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. These may be used alone or in combination of two or more.

  The physical properties of the component (a1-2) are not particularly limited. Usually, the weight average molecular weight is about 100 to 350 and the hydroxyl value is about 480 to 1100 mgKOH / g, preferably about 150 to 250, and 600 to 1000 mgKOH in order. / G or so. Moreover, when the repeating unit derived from the said alkylene oxide is introduce | transduced into this (a1-2) component, the repeating number (f) is although it does not specifically limit, Usually, it is about 0-3. In addition, this (a-2) component may be a commercial item.

  Examples of the diamine represented by the general formula (2) constituting the component (a1-3) include ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3-propanediamine, and 2-methyl. -1,5-pentanediamine, 1,3-diaminopentane, 2,2,4- or 2,4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8 -Aliphatic diamines such as octanediamine, 1,9-nonanediamine, 1,10-decanediamine, isophoronediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 4,4 Alicyclic diamines such as' -dicyclohexylmethanediamine, tolylenediamine, xylylenediamine and 4,4'-di They include aromatic diamines such as E methane diamine, these may be used alone or in combination of two or more. Specific examples of the alkylene oxide to be subjected to addition reaction with the diamine include those described above.

  The physical properties of the component (a1-3) are not particularly limited. Usually, the weight average molecular weight is about 290 to 560, and the hydroxyl value is about 400 to 900 mgKOH / g, preferably about 290 to 400, and 600 to 800 KOH / It is about g. Moreover, when the repeating unit derived from the said alkylene oxide is introduce | transduced into this (a1-3) component, the repeating number (f) is although it does not specifically limit, Usually, it is about 1-3.

  In addition, this (a-3) component may be a commercial item, for example, New Pole NP-300 (manufactured by Sanyo Chemical Co., Ltd.), GR-04 (manufactured by Mitsui Chemicals, Inc.) and the like.

  In addition, the component (a1) may include other polyether polyols obtained by addition reaction of ammonia, various known monoamines, and polyamines having 4 or more amino groups as initiators. . Examples of the monoamine include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, aniline diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, and tributylamine; monomethanolamine, monoethanolamine, mono Alkanol monoamines such as propanolamine and monobutanolamine, dimethanolamine, diethanolamine, dipropanolamine and dibutanolmonoamine may be used, and these may be used alone or in combination of two or more. Examples of the polyamine having 4 or more amino groups include triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

  The component (a2) is a diol having a phosphorus atom in the molecule, and contributes to improving the thin flame retardancy by carbonizing itself. It also contributes to heat resistance.

  As the component (a2), various known compounds can be used without particular limitation as long as they are diols having a phosphorus atom in the molecule. In the narrow sense, it does not have an amino group in the molecule. As the component (a2), specifically, for example, those represented by the following general formula are preferable.

(In the formula (4), R ⁴ represents an alkyl group having 1 to 20 carbon atoms or an aryl group optionally substituted with the alkyl group. Also, R ⁵ , R ⁶ and R ⁷ are all carbon atoms. 1 to 3 represents an alkylene group, and m represents an integer of 0 to 4.)

Specific examples of the compound represented by the general formula ( 4 ) include, for example, diisopropyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, diisobutyl-N, N-bis (2-hydroxyethyl) amino. Methylphosphonate, dioctyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, dioctadecyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, diethyl-N, N-bis (2-hydroxyethyl) ) Aminomethylphosphonate, diethyl-N, N-bis [2- (2-hydroxyethoxy) ethyl] aminomethylphosphonate, diethyl-N, N-bis [ω- (2-hydroxy) polyethoxyethyl] aminomethylphosphonate, Diethyl-N, N-bis (2-hydroxypropyl) amino Nomethylphosphonate and the like, and these may be used alone or in combination of two or more. Of these, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate is particularly preferred.

  In addition, this (a2) component may be a commercial item, for example, ADEKA polyol FC-450 (made by ADEKA), M-Ester-HP (made by Sanko Co., Ltd.), Y-24 (Sanyo Chemical ( Etc.).

  The component (a3) is a polyol for polyurethane, and various known ones can be used without particular limitation as long as they do not correspond to both the component (a2) and the component (a3). Specifically, for example, various known low molecular weight polyols (non-polymers) and the low molecular weight polyols as initiators are added to the alkylene oxide represented by the general formula (3). Polyols (polymers) such as polyether polyol (a3-1) (hereinafter referred to as component (a3-1)), polyester polyol, polycarbonate polyol, polyolefin polyol, and the like can be given.

  Examples of the low molecular weight polyols include 1,2-propanediol, 1,3-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, Of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A Diols such as ethylene oxide adduct, catechol, resorcinol, hydroquinone, xylylene glycol and bishydroxyethoxybenzene, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1 Triols such as 2,4-butanetriol, cyclohexanetriol, pyrogallol and phloroglucinol, tetraols such as diglycerol erythritol, sorbitol, pentaerythritol and dipentaerythritol, D-arabinitol, L-arabinitol, ribitol, xylitol, Examples include hexavalent or higher alcohols such as dipentaerythritol.

  As said (a3-1) component, various well-known things can be especially used without a restriction | limiting, For example, at least 1 sort (s) of poly selected from the group which consists of a polyoxypropylene polyol, a polyoxyethylene polyol, and a polyoxyethylene propylene polyol. And oxyalkylene polyols. The number of repetitions (f) is not particularly limited, but is usually about 1 to 30, preferably about 1 to 7, and more preferably about 1 to 3. In addition, the component (a3-1) may be a commercially available product, such as OK All 93 (Okabata Sangyo Co., Ltd.), Brownon TMP-20, Brownon TMP-1, Brownon GL-3, Brownon GL-9, BROWNON GL-20, BROWNON GL-26, BROWNON 240 (above, manufactured by Aoki Oil & Fat Co., Ltd.), UNIOX G-450, UNIOX G-750, UNIOR TG-330, UNIOR TG-1000, UNIOR TG-2000, Uniol HS-1600 (above, manufactured by NOF Corporation), DSC-E450, SC-E750, SC-E1000, SC-E1500, SC-E2000 (above, manufactured by Sakamoto Pharmaceutical Co., Ltd.), GP-400, GP-600, TP-400, TP-700, PP-3000 (above, manufactured by Sanyo Kasei Co., Ltd.), Adeka Polyate P-3000 ((Ltd.) ADEKA), and the like. Particularly, the (poly) oxyalkylene polyol is a polyether polyol obtained by addition-reacting the triols or tetraols with an alkylene oxide represented by the general formula (3), and the repeating number (f) is 1. Those of about ~ 3 are preferred.

  Examples of the polyester polyol include those obtained by dehydrating and condensing the diols and various known dicarboxylic acids. Examples of the dicarboxylic acids include adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, and suberic acid. And dimer acids, anhydrides of corresponding ones thereof, alkyl esters thereof, and the like. These may be used alone or in combination of two or more.

  Examples of the polycarbonate polyol include a condensate of the low molecular weight polyols and dimethyl carbonate, a condensate of the low molecular weight polyols and diphenyl carbonate, a condensate of the low molecular weight polyols and ethylene carbonate, and the like.

  Examples of the polyolefin polyol include polybutadiene polyol and polyisoprene polyol having a hydroxyl group at the terminal, or hydrogenated products thereof.

  Although the molecular weight of the polyol is not particularly limited, it is usually about 180 to 5000, preferably about 180 to 3000, and more preferably about 180 to 1000, considering the balance of thin flame retardancy, impact resistance and heat resistance. .

  As the component (a3), an appropriate one can be selected depending on the use of the composition according to the present invention, but the component (a3-1) is particularly preferable from the viewpoint of thin flame retardancy and impact resistance.

  The content of the (a1) component (a2) component and the (a3) component in the component (A) is not particularly limited, but is usually about 40 to 70% by weight in order from the viewpoint of thin flame retardancy and impact resistance. They are about 20 to 50% by weight and about 1 to 20% by weight, preferably about 50 to 60% by weight, about 30 to 40% by weight and about 5 to 15% by weight.

  (B) As a component, various well-known polyisocyanate compounds are mentioned. Specifically, for example, aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1, Alicyclic diisocyanates such as 4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated tolylene diisocyanate; toluene-2,4,6-triisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, 1, 6,11-undecane triisocyanate, 1,3,6-hexamethylene Triisocyanates such as isocyanate and bicycloheptane triisocyanate; derivatives of the diisocyanates (uretidione, carbodiimide, TMP adduct, isocyanurate, burette, allophanate, etc.) (product names “Coronate L”, “Coronate HL”) ”,“ Coronate HX ”, etc., manufactured by Nippon Polyurethane Industry Co., Ltd.); tetraisocyanate compound formed by linking two molecules of the derivative with one molecule of the diol; hexafunctional polyisocyanate (product name“ Duranate MHG-80B ”) Asahi Kasei Chemicals Co., Ltd.): An isocyanate group-terminated prepolymer (hereinafter referred to as component (b1)) obtained from the derivative of the diisocyanates and the component (a3-1), and the like. It may be used alone or two or more It may be used in combination. Among these, the component (b1) is particularly preferable from the viewpoint of thin flame retardancy and impact resistance.

  As the diisocyanate derivative constituting the component (b1), a carbodiimide body of an aromatic diisocyanate is preferable. Specifically, a composition containing diphenylmethane diisocyanate and its carbodiimide body (see the following structural formula) is preferable.

  The component (a3-1) constituting the component (b1) is preferably at least one selected from the group consisting of polyoxypropylene glycol, polyoxyethylene glycol, and polyoxyethylene / propylene glycol. Further, the molecular weight of the component (a3-1) is not particularly limited, but considering the balance of thin flame retardancy, impact resistance and heat resistance, the weight average molecular weight is usually about 1000 to 5000, preferably 2000 to 4000. Degree.

  The conditions for the urethanization reaction between the diisocyanates constituting the component (b1) and the component (a3-1) are not particularly limited. Usually, the number of moles of the former hydroxyl group (OH ′) and the latter isocyanate group The ratio (NCO ′ / OH ′) to the number of moles (NCO ′) is about 0.05 to 0.15, the reaction temperature is about 40 to 80 ° C., and the reaction time is about 0.5 to 2 hours. Further, the isocyanate group concentration of the component (b1) (the ratio of the isocyanate group weight to the total weight of the component (b1)) is not particularly limited, but is usually about 20 to 25%.

(C) component is an essential component of the composition which concerns on this invention with (D) component mentioned later, and various well-known things can be especially used without a restriction | limiting. Examples of the component (C), especially from the viewpoint of thin flame retardant, in particular acyclic polyphosphate Fazen compound having a repeating unit represented by in the molecule by the following general formula (5) and / or the following general formula (6) in cyclic phosphite Fazen compound represented it is preferred.

(In the formula (5), R ⁷ represents any of an alkyl group having 1 to 20 carbon atoms, an aryl group which may be substituted with the alkyl group, and an aryloxy group which may be substituted with the alkyl group. Show.)

(In Formula (6), R ⁸ represents any of an alkyl group having 1 to 20 carbon atoms, an aryl group optionally substituted with the alkyl group, and an aryloxy group optionally substituted with the alkyl group. Show.)

  Component (C) may be a commercially available product. For example, SPS-100, SPB-100, SPB-100L, SPE-100 (above, manufactured by Otsuka Chemical Co., Ltd.), FP-100 (Fushimi Pharmaceutical Co., Ltd.) Etc.

  As the component (D), various known materials can be used without particular limitation as long as they are calcined polytetrafluoroethylene particles. In this invention, it is thought that the film which consists of a polyurethane resin of this invention shrinks at the time of combustion by using not only the said (C) component but this (D) component, and combustion dripping decreases. Conversely, when the component (D) is not used, or when non-fired polytetrafluoroethylene particles are used instead of the component (D), the thin flame retardancy tends to be poor.

  The particle size of the component (D) is not particularly limited, but the maximum average primary particle size is usually about 5 to 150 μm and the median diameter (d50) is about 3 to 40 μm, especially considering thin flame retardancy. is there. Moreover, it is about 5-20 micrometers preferably in order, and is about 3-7 micrometers. Moreover, (D) component may be a commercial item, for example, KTL-8N, KTL-10N, KTL-20N (above, product made from Kitamura Co., Ltd.) etc. are mentioned.

  The component (E) is an optional component used to accelerate the curing reaction of the component (A) and the component (B) and improve the thin flame retardancy and impact resistance of the polyurethane resin according to the present invention. , Organic metal catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and bismuth octylate, and organic amine catalysts such as diazabicyclooctane, dimethylcyclohexylamine, tetramethylpropylenediamine, ethylmorpholine, dimethylethanolamine, triethylamine and triethylenediamine , N-methylimidazole, 1,2-dimethylimidazole, imidazole catalysts such as 1,3 dimethylimidazole, and the like. These may be used alone or in combination of two or more.

  In addition, various additives can be included in the composition of the present invention as necessary. Specifically, for example, dehydrating agents, masking materials, pigments, dyes, antifoaming agents, leveling agents, antistatic agents, flame retardants (excluding those corresponding to the components (C) and (D)), and stable. And the like.

  The amount ratio of the component (A) and the component (B) in the composition of the present invention is not particularly limited. However, considering the balance between thin flame retardancy, impact resistance and heat resistance, the former is usually the number of moles of hydroxyl group. The ratio (NCO / OH) of (OH) to the number of moles of isocyanate groups (NCO) of the latter is about 0.9 to 1.5, preferably about 0.95 to 1.2.

  Further, the contents of the component (A), the component (B), the component (C) and the component (D), and the component (E) and additives used as necessary in the composition of the present invention are not particularly limited. Considering the balance of flame retardancy, impact resistance, flex resistance, etc., the following are usually as follows.

Component (A): Usually about 25 to 55% by weight, preferably about 30 to 45% by weight (B) Component: Usually about 30 to 60% by weight, preferably about 35 to 50% by weight (C) Component: Usually 1 to 1 About 10% by weight, preferably about 1 to 7% by weight (D) Component: usually about 3 to 15% by weight, preferably about 5 to 10% by weight (E) Component: usually about 0.001 to 1% by weight, preferably 0.001 to 0.5% by weight
Additive: Usually about 0 to 15% by weight, preferably about 1 to 10% by weight

  The composition of the present invention is obtained by kneading the component (A), the component (B), the component (C) and the component (D), the component (E) used as necessary, and the additive by various known means. can get. At that time, all the components may be kneaded at once, or both of them may be kneaded separately into a main agent essentially comprising the component (A) and a curing agent essentially comprising the component (B). In the case of such a two-component embodiment, the component (C) and the component (D), the component (E) used as necessary, and the additive may be included in one or both of the main agent and the curing agent.

  The flame retardant polyurethane resin of the present invention is obtained by thermosetting the composition of the present invention. The mode of thermosetting is not particularly limited, and various known molding methods can be employed, for example. Specifically, compression molding method, transfer molding method, jet molding method, injection molding method, blow molding method, vacuum method, compression processing method, welding processing method, printing processing method, in-mold molding method, shell mold molding method Etc. Further, the form of the polyurethane resin is not particularly limited, and may be linear, plate-like, or three-dimensional. Further, when molding, it may be integrally molded together with some parts (such as electronic parts). Further, the polyurethane resin can be used as a jacket material such as a battery pack described later, a casing of various electric / electronic devices, and a package of those components.

  The flame-retardant article of the present invention is a material comprising the flame-retardant polyurethane resin of the present invention and is obtained from the composition of the present invention, and therefore exhibits excellent thin flame retardancy. Specifically, as described above, the UL94-VTM test indicates VTM-2, preferably VTM-1, and most preferably VTM-0. In addition, shrinkage and drip are less likely to occur when burned.

  The battery housing of the present invention is an embodiment of the flame-retardant article of the present invention, and can be preferably used as a case (pack) for various batteries such as lithium ion batteries, as well as housings for electronic and electrical equipment, It is also suitable as a package for various parts.

  Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. “Parts” is based on parts by weight.

Production Example 1
(Production of component (b1))
In a flask equipped with a stirrer and a thermometer, 82 parts (trade name “Coronate MX”, manufactured by Nippon Polyurethane Industry Co., Ltd.) of carbodiimide of diphenylmethane diisocyanate (produced by Nippon Polyurethane Industry Co., Ltd.), commercially available polypropylene glycol ( 18 parts of a trade name “PP-3000”, a weight average molecular weight of 3000, manufactured by Sanyo Chemical Industries Co., Ltd.) were added and stirred at 60 ° C. with heating. Next, 0.005 part of a commercially available antifoaming agent (trade name “KP-330”, manufactured by Shin-Etsu Chemical Co., Ltd.), a commercially available stabilizer (methyl acid phosphate, trade name “AP-1”, Daihachi An isocyanate group-terminated prepolymer composition was produced by adding 0.001 part of Kogyo Kogyo Co., Ltd. and stirring under heating at 70 ° C. for 1 hour.

Example 1
46.62 parts of a commercially available nitrilotris alkanol (trade name “Leocon MA-170”, manufactured by Lion Corporation) as the component (a1), a commercially available phosphorus-containing diol (trade name “FC-450”) as the component (a2), 28.67 parts (manufactured by ADEKA Corporation), commercially available polyether polyol (ethylene oxide adduct of trimethylolpropane, weight average molecular weight of about 185, component name “Brownon TMP-1”, Aoki Yushi Co., Ltd.) as component (a3) Manufactured) 10.85 parts, (C) commercially available calcined polytetrafluoroethylene particles (trade name “KTL-8N”, manufactured by Kitamura Co., Ltd., maximum average primary particle diameter 11 μm, median diameter 3.61 μm) 0 .93 parts, commercially available imidazole urethane catalyst (trade name “NC-IM”, manufactured by Nippon Emulsifier Co., Ltd.) as component (E) 0.01 Parts, and 0.93 part of a commercially available dehydrating agent (trade name “L Paste”, manufactured by Union Showa Co., Ltd.) as an additive, an antifoaming agent (trade name “BYK-506”, manufactured by Big Chemie Japan Co., Ltd.) 0.07 parts and 6.34 parts of a concealing material (carbon black master) (trade name “VM-12”, manufactured by Pernox Co., Ltd.) were kneaded to prepare a main agent. Next, 90.9 parts of (b1) component obtained in Production Example 1 and 6.00 parts of commercially available cyclic phosphazene (trade name “SPS-100”, manufactured by Otsuka Chemical Co., Ltd.) as component (D) and also commercially available Cyclic phosphazene (trade name “SPB-100L”, manufactured by Otsuka Chemical Co., Ltd.) 7.00 parts, and a commercially available phosphorus plasticizer (trade name “TKP”, manufactured by LANXESS) 9.10. The parts were kneaded to prepare a curing agent. Then, the main agent and the curing agent were kneaded to prepare a thermosetting composition.

(Evaluation of thin flame retardancy)
Next, the thermosetting composition was poured into a mold heated to 70 ° C. using a two-component mixing dispenser and heated for 15 minutes to obtain a polyurethane resin film having a thickness of 0.15 mm. Next, a film test piece (200 mm × 50 mm × 0.15 mm) was cut out from the film according to the standard (ASTM D4804) of the thin material vertical combustion test (UL94VTM). Next, a combustion test was performed according to the standard using the test piece, and VTM-2, VTM-1, VTM-0 and Not were determined based on the combustion behavior. In addition, among the combustion behavior, the shrink tendency and the drip tendency were separately visually determined according to the following criteria.

Shrinking tendency 1: The test piece shrinks greatly.
2: The specimen slightly shrinks.
3: The test piece does not shrink.

Drip tendency 1: no burning drop from test piece.
2: 1 to 2 drops of combustion drop are observed from the test piece, and the drop does not ignite cotton.
3: Three or more drops of combustion drops are seen from the test piece, and cotton drops are ignited by the drops.

(Evaluation of impact resistance)
In accordance with JIS K 7110 (Izod impact test), a test piece (No. 2 test piece A notch) was prepared using the thermosetting composition of Example 1. In addition, the dimension of this test piece was 64.0 mm x 12.7 mm x 12.7 mm. The notch dimensions were a tip radius of 0.25 mm and a depth of 2.54 mm. Next, one end of the test piece was fixed with a fixed tightening pressure, the hammer fixed at a predetermined position from the direction of the notch was gently dropped, the test piece was broken with one blow, and the swing angle at that time was read. . The absorbed energy was calculated from this angle, and the Izod impact strength (KJ / m ² ) was further determined.

(Evaluation of deflection temperature under load)
A test piece (dimensions: 120.0 mm × 10.0 mm × 10.0 mm) was prepared using the thermosetting composition of Example 1 in accordance with JIS K 7191-1 (Plastic—How to determine the deflection temperature under load). did. Next, using a commercially available testing machine (product name “TP-101 Heat Distortion Tester (HDT Tester)”, manufactured by Tester Sangyo Co., Ltd.), the temperature at the time of bending of the test piece was measured under a bending stress of 0.45 MPa. It was measured.

(Evaluation of bending strength)
A test piece (dimensions: 80.0 mm × 10.0 mm × 4.0 mm) was prepared using the thermosetting composition of Example 1 in accordance with JIS K 7171 (Plastic—How to determine bending properties). Next, using a commercially available testing machine (product name “Autograph AGS-X”, manufactured by Shimadzu Corporation), a load was applied at a head speed of 5 mm / min, and the maximum load was recorded.

(Evaluation of flexural modulus)
A test piece (dimensions: 80.0 mm × 10.0 mm × 4.0 mm) was prepared using the thermosetting composition of Example 1 in accordance with JIS K 7171 (Plastic—How to determine bending properties). Next, using a commercially available testing machine (product name “Autograph AGS-X”, manufactured by Shimadzu Corporation), a load was applied at a head speed of 5 mm / min, and the flexural modulus was measured from the slope of the load-deflection curve. .

Examples 2 to 10 and Comparative Examples 1 to 4
A base resin and a curing agent were prepared in the same manner as in Example 1 except that the raw materials and the number of parts used were changed as shown in Table 1, and a thermosetting composition was prepared to produce a polyurethane resin film. Subsequently, the same test as Example 1 was implemented about each of this film. The results are shown in Table 1. In Table 1, “KTL-10N” represents commercially available calcined polytetrafluoroethylene particles (trade name, manufactured by Kitamura Co., Ltd., maximum average primary particle diameter 31 μm, median diameter 10.2 μm), and “KTL-20N”. “Commercially baked polytetrafluoroethylene particles (trade name, manufactured by Kitamura Co., Ltd., maximum average primary particle diameter 44 μm, median diameter 16.1 μm),“ KTL-8F ”is commercially available non-baked polytetrafluoroethylene. It means ethylene particles (trade name, manufactured by Kitamura Co., Ltd., maximum average primary particle diameter 13 μm, median diameter 3.28 μm), respectively.

Claims (11)

The following general formula (4)
(In the formula (4), R ⁴ represents an alkyl group having 1 to 20 carbon atoms or an aryl group optionally substituted with the alkyl group. Also, R ⁵ , R ⁶ and R ⁷ are all carbon atoms. 1 to 3 represents an alkylene group, and m represents an integer of 1 to 4.)
In represented by polyols containing compound (A), the polyisocyanate (B), containing a phosphazene compound (C) and calcined type polytetrafluoroethylene particles (D), and a urethane catalyst optionally (E), the flame Thermosetting composition for flammable polyurethane resin. The composition of claim 1, wherein the component (A) comprises an amino group-containing polyol (a1) and a polyol (a3) other than these. The component (a1) is a nitrilotris alkanol (a1-1) represented by the following general formula (1), an alkylene oxide represented by the following general formula (3) using the (a1-1) component as an initiator Addition reaction of a polyether polyol (a1-2) obtained by addition reaction with an alkylene diamine represented by the following general formula (2) and an alkylene oxide represented by the following general formula (3). The composition according to claim 2, which is at least one polyol selected from the group consisting of polyether polyols (a1-3).
(In formula (1), R ¹ represents hydrogen or a methyl group, respectively.)
(In formula (2), R ² represents an alkylene group having 2 to 4 carbon atoms.)
(In formula (3), R ³ represents hydrogen or an alkyl group having 1 to 3 carbon atoms.) The component (a3) is a polyether polyol (a3-1) obtained by addition-reacting an alkylene oxide represented by the general formula (3) with a low molecular weight polyol as an initiator. Any of the compositions. The composition according to claim 4, wherein the component (B) is an isocyanate group-terminated prepolymer (b1) obtained by reacting a diisocyanate with the component (a3-1). The component (C) is an acyclic polyphosphazene compound having a repeating unit represented by the following general formula (5) in the molecule and / or a cyclic phosphazene compound represented by the following general formula (6). The composition of any of 5.
(In the formula (5), R ⁷ represents any of an alkyl group having 1 to 20 carbon atoms, an aryl group which may be substituted with the alkyl group, and an aryloxy group which may be substituted with the alkyl group. Show.)
(In Formula (6), R ⁸ represents any of an alkyl group having 1 to 20 carbon atoms, an aryl group optionally substituted with the alkyl group, and an aryloxy group optionally substituted with the alkyl group. Show.) (D) The composition in any one of Claims 1-6 whose maximum average primary particle diameter of a component is 5-150 micrometers, and whose median diameter (d50) is 3-40 micrometers. (E) A component is an imidazole type compound, The composition in any one of Claims 1-7. A flame retardant polyurethane resin obtained by thermosetting the composition according to claim 1. A flame-retardant article comprising the flame-retardant polyurethane resin according to claim 9. A battery pack comprising the flame-retardant polyurethane resin according to claim 9.