FIRE-RESISTANT THERMOPLASTIC POLYURETHANE ELASTOMER COMPOSITION

专利摘要:
Fire Resistant Thermoplastic Polyurethane Elastomer Composition This fire resistant thermoplastic polyurethane elastomer composition is obtained by adding component (a), component (b), and component (c) to a thermoplastic polyurethane elastomer. (a) is a (poly)phosphate compound represented by the general formula (1), (b) is a (poly)phosphate compound represented by the general formula (3), and (c) is silicon dioxide. this fire resistant thermoplastic polyurethane elastomer composition preferably further contains (d) zinc oxide as component (d). see report for definitions of n, x1 , and p in formula (1). see report for definitions of r, y1 and q in formula (3).
公开号:BR112016023206B1
申请号:R112016023206-2
申请日:2015-02-18
公开日:2021-09-08
发明作者:Ni YANG；Shimizu Tatsuya
申请人:Adeka Corporation；
IPC主号:

专利说明:

TECHNICAL FIELD
[0001] This invention relates to a thermoplastic polyurethane elastomer composition having excellent fire resistance with specific resin physical properties intact. TECHNICAL BACKGROUND
[0002] Thermoplastic polyurethane (TPU) elastomers are composed of easily mobile long-chain units called soft segments and extremely crystalline units called hard segments and exhibit excellent physical properties attributed to their characteristic structure, such as elasticity, elongation, mechanical strength and strength to abrasion. With these physical properties regarded as advantageous, they have been used in various fields such as, for example, hoses, belts, wires, cables, tubes, soles, automobile interior and exterior finishes and various moldings.
[0003] A fire resistance agent is mixed with a TPU to impart fire resistance to the TPU. The use of a halogen fire resistance agent has the problem of generating harmful gas in combustion. It is known to use, in place of a nitrogen and/or phosphorus containing compound, such as melamine phosphate, melamine polyphosphate, or a condensed phosphoric ester, as a halogen-free fire resistance agent (see patent document 1, below) .
[0004] It is also proposed to use a swellable phosphate fire resistance agent that induces formation of a swollen surface layer in combustion, which prevents diffusion of a decomposition product and heat transfer so as to achieve fire resistance ( see patent document 2).
[0005] However, conventional phosphate-based fire resistance agents must be added in large amounts, in order to obtain sufficient fire resistance, which can result in damage to the resin's intrinsic physical properties. The use of an anti-drip agent such as polytetrafluoroethylene, which is added to prevent dripping, can also damage the resin's intrinsic physical properties. LIST OF QUOTES PATENT DOCUMENT Patent Document 1: JP 2001-49053A Patent Document 2: WO 2010/013400 SUMMARY OF THE INVENTION TECHNICAL PROBLEM
[0006] An object of the invention is to provide a TPU elastomer with high fire resistance and excellent physical properties intrinsic to the resin without using a halogen fire resistance agent that generates a harmful gas in combustion and a fluorine anti-drip agent .
[0007] Another object of the invention is to provide a molded article that has high fire resistance and excellent physical properties intrinsic to the resin and that does not emit any harmful gas of halogen origin in combustion. SOLUTION TO THE PROBLEM
[0008] As a result of extensive research, the inventors completed the present invention.
[0009] The invention provides a fire resistant thermoplastic polyurethane elastomer composition comprising a thermoplastic polyurethane elastomer, (A) a (poly)phosphate compound represented by the general formula (1) below, (B) a (poly) compound )phosphate represented by the general formula (3) below and (C) silicon dioxide.
[Chemical formula 1] where n represents a number from 1 to 100; X1 represents ammonia or a triazine derivative having general formula (2) below, and p represents a number having regard to: 0<p<n+2;
[Chemical formula 2] wherein Z1 and Z2, which may be the same or different, each represent a group selected from the group consisting of -NR5R6 (wherein R5 and R6, which may be the same or different, each represents a hydrogen atom , a linear or branched alkyl group having 1 to 6 carbon atoms, or a methylol group), a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group, and a vinyl group; and [Chemical formula 3]
[Chemical formula 3] where r represents a number from 1 to 100; Y1 represents a diamine represented by R1R2N(CH2)mNR R4, piperazine, or a diamine having a piperazine ring, wherein R1, R2, R3, and R4, which may be the same or different, each represent a hydrogen atom or a group straight or branched alkyl having 1 to 5 carbon atoms; m represents an integer from 1 to 10; eq represents a number given the relationship: 0<q<r+2.
[0010] The fire resistant TPU elastomer composition of the invention preferably contains (D) zinc oxide.
[0011] Component (A) of the fire resistant TPU elastomer composition of the invention is preferably melamine pyrophosphate which is the compound of general formula (1) wherein n is 2, p is 2, and X1 is melamine (i.e. , the compound of general formula (2) wherein Z1 and Z2 are each -NH2).
[0012] Component (B) of the fire resistant TPU elastomer composition of the invention is preferably a piperazine polyphosphate which is the compound of general formula (3) wherein q is 1, and Y1 is piperazine.
[0013] Piperazine polyphosphate as component (B) of the fire resistant TPU elastomer composition of the invention is preferably piperazine pyrophosphate.
[0014] The molded article of the invention is obtained from the fire resistant TPU elastomer composition of the invention. EFFECT OF THE INVENTION
[0015] The invention provides a TPU elastomer with high fire resistance and excellent physical properties intrinsic to the resin without using a halogen fire resistance agent that generates a harmful gas in combustion and a fluorine anti-drip agent. The invention also envisages a molded article that exhibits high fire resistance and excellent physical properties intrinsic to the resin and does not emit any harmful halogen-origin gas in combustion. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 is a photograph showing a swollen surface layer of the test sample obtained in Example 1.
[0017] Figure 2 is a photograph showing a swollen surface layer of the test sample obtained in Comparative Example 1. DESCRIPTION OF MODALITIES
[0018] The TPU elastomer that can be used in the fire resistant TPU elastomer of the invention will be described first.
[0019] The TPU elastomer for use in the invention is generally prepared using a polyol, a diisocyanate, and a chain extender. Examples of the polyol include polyester polyols, polyester ether polyols, polycarbonate polyols and polyether polyols.
[0020] Examples of polyester polyols include those obtained by dehydration and condensation between an aliphatic dicarboxylic acid (eg succinic acid, adipic acid, sebacic acid, or azelaic acid), an aromatic dicarboxylic acid (eg phthalic acid, terephthalic acid , isophthalic acid, or naphthalenedicarboxylic acid), an alicyclic dicarboxylic acid (for example, hexahydrophthalic acid, hexahydroterephthalic acid, or hexahydroisophthalic acid), or an acid ester or anhydride thereof and ethylene glycol, 1,3-propylene glycol, 1,2 -propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,3-octanediol, 1.9 -nonanediol, or a polyol type, or a mixture of these polyols; and polylactone diols obtained by ring-opening polymerization of a lactone monomer such as ε-caprolactone.
[0021] Examples of polyester ether polyols include those obtained by dehydration and condensation between an aliphatic dicarboxylic acid (eg succinic acid, adipic acid, sebacic acid, or azelaic acid), an aromatic dicarboxylic acid (eg phthalic acid, acid terephthalic acid, isophthalic acid, or naphthalenedicarboxylic acid), an alicyclic dicarboxylic acid (for example, hexahydrophthalic acid, hexahydroterephthalic acid, or hexahydroisophthalic acid), or an acid ester or anhydride thereof and a glycol, such as diethylene glycol or an oxide adduct. propylene, or a mixture of these glycols.
[0022] Examples of polycarbonate polyols include those obtained by the reaction between at least one polyhydric alcohol (eg ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol , 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, or diethylene glycol) and diethylene carbonate, dimethyl carbonate , diethyl carbonate, or the like.
[0023] Copolymers of polycaprolactone polyol (PCL) and polyhexamethylene carbonate (PHL) are also usable.
[0024] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol, which are each obtained by polymerizing a cyclic ether (eg, ethylene oxide, propylene oxide, and tetrahydrofuran, respectively), and their copolyethers.
[0025] Examples of the diisocyanate include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), tolidine diisocyanate, 1,6-hexamethylene diisocyanate (HDI ), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hydrogenated XDI triisocyanate, tetramethylxylene diisocyanate (TMXDI), 1,6,11-undecane triisocyanate, methyloctane 1,8-diisocyanate, lysine triisocyanate ester , 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, and dicyclohexylmethane diisocyanate (hydrogenated MDI, or HMDI). Preferred among these are 4,4'-diphenylmethane diisocyanate (MDI) and 1,6-hexamethylene diisocyanate (HDI).
[0026] A low molecular weight polyol can be used as the chain extender in the preparation of the TPU elastomer. Examples of the low molecular weight polyol include aliphatic polyols such as ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, 1,4-cyclohexanedimethanol, and glycerol; and aromatic glycols such as 1,4-dimethyrol benzene, bisphenol A, and bisphenol A ethylene oxide or propylene oxide adducts.
[0027] TPU elastomer types include ester-based polyurethane copolymers (lactone-based), ester-based polyurethane copolymers (adipate-based), ether-based polyurethane copolymers, polyurethane-based copolymers carbonate based, and ether/ester based polyurethane copolymers. Examples of commercially available (lactone-based) polyurethane ester copolymers include Elastollan C80A10 (from BASF Japan), Elastollan C80A50 (from BASF Japan) and Resamine P-4000 and P-4500 series (from Dainichiseika Color & Chemicals Mfg Co., Ltd.). Examples of commercially available ester-based polyurethane copolymers (adipate-based) include Pandex T-5000V (DIC Bayer Polymer Ltd.), Pandex TR-3080 (from DIC Bayer Polymer Ltd.), and Resamine P-1000 series and P-7000 (from Dainichiseika Color & Chemicals Mfg. Co., Ltd.). Examples of commercially available ether-based polyurethane copolymers include Elastollan 1180A50 (from BASF Japan Ltd.), Pandex T-8180 (from DIC Bayer Polymer Ltd.), Pandex T-8283 (from DIC Bayer Polymer Ltd.), Pandex T - 1190 (from DIC Bayer Polymer Ltd.), and Resamine P-2000 series (from Dainichiseika Color & Chemicals Mfg. Co., Ltd.). Examples of commercially available carbonate-based polyurethane copolymers include Pandex T-7890N (from DIC Bayer Polymer Ltd.). Examples of commercially available ether/ester-based polyurethane copolymers include Desmopan DesKU2-88586 (from DIC Bayer Polymer Ltd.) and Resamine P-800 series (from Dainichiseika Color & Chemicals Mfg. Co.). These TPU elastomers can be used alone or in combination.
[0028] Component (A) in the invention will then be described.
[0029] The (poly)phosphate compound having general formula (1), which is used as component (A) in the invention, is a salt formed between a (poly)phosphoric acid and ammonia or a triazine derivative represented by the general formula (two).
[0030] Examples of linear or branched C1-C10 alkyl group as represented by Z1 and Z2 in formula (2) include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t -amyl, hexyl, cyclohexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, nonyl and decyl. Examples of the linear or branched C1-C10 alkoxy group include those derived from the alkyl groups described above. Examples of the linear or branched C1-C6 alkyl group as R5 and R6 of -NR5R6 represented by Z1 and Z2 include those having up to 6 carbon atoms among the alkyl groups described above.
[0031] Examples of the triazine derivative include melamine, acetoguanamine, benzoguanamine, acrylguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5- -triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy -1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino -6-mercapto-1,3,5-triazine, and 2-amino-4,6-dimercapto-1,3,5-triazine.
The (poly)phosphate compound of formula (1) which can be preferably used as component (A) is exemplified by a salt between a (poly)phosphoric acid and melamine or an ammonium polyphosphate compound.
[0033] Examples of the salt of (poly)phosphoric acid and melamine, which is preferably used, include melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate. Particularly preferred among them is melamine pyrophosphate having formula (1) where n is 2, p is 2, and X1 is melamine. The salt between a phosphoric acid and melamine can be obtained by the following process. Melamine pyrophosphate, for example, can be obtained by causing sodium pyrophosphate and melamine to react with each other at any rate in the presence of hydrochloric acid, followed by neutralization with sodium hydroxide.
[0034] The term "ammonium polyphosphate compound" is intended to encompass single ammonium polyphosphate and a compound comprising primarily ammonium polyphosphate. As the only ammonium polyphosphate, commercially available products can be used, including Exolit 422 and Exolit 700 (both from Clariant Japan), Phos-Chek P/30 and Phos-Chek P/40 (both from Monsanto Co.), Sumisafe P ( from Sumitomo Chemical Co., Ltd.), and Terraju S10 and S20 (both from Chisso Corp.).
[0035] Examples of the compound primarily comprising ammonium polyphosphate include ammonium polyphosphate coated or microencapsulated with a thermoforming resin, ammonium polyphosphate coated with an organic nitrogen-containing compound such as melamine monomer, ammonium polyphosphate treated with a surfactant or silicone , and poorly soluble ammonium polyphosphate obtained by adding melamine to a system for preparing ammonium polyphosphate.
[0036] Examples of commercially available compounds primarily comprising ammonium polyphosphate include Exolit 462 from Clariant, Sumisafe PM from Sumitomo Chemical, and Terraju C60, C70, and C80 from Chisso.
[0037] Component (A) may be a mixture of two or more compounds.
[0038] Component (B) in the invention will be described below.
[0039] The (poly)phosphate compound having general formula (3), which is used as component (B) in the invention, is a salt formed between a (poly)phosphoric acid and a diamine represented by Y1 (specifically, a diamine represented by [R1R2N(CH2)mNR3R4], piperazine, or a diamine containing piperazine ring). The linear or branched C1-C5 alkyl group as represented by R1, R2, R3 and R4 is exemplified by those having 1 to 5 carbon atoms among the alkyl groups described above as Z1 and Z2.
[0040] Examples of the diamine as Y1 in formula (3) include N,N,N',N'-tetramethyldiaminomethane, ethylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N-dimethylethylenediamine, N, N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-diethylethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylene diamine, pentamethylenediamine, hexamethylenediamine, 1 ,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, piperazine, trans-2,5-dimethylpiperazine, 1,4-bis(2-aminoethyl)piperazine, and 1,4 -bis(3-aminopropyl)piperazine. Any commercially available product of these diamines can be used.
The (poly)phosphate compound of formula (3), which is preferably used as component (B), is exemplified by a salt between a (poly)phosphoric acid and piperazine. Examples of the salt between a (poly)phosphoric acid and piperazine include piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate. Preferred among them are piperazine polyphosphates of formula (3) wherein q is 1 and y1 is piperazine, particularly piperazine pyrophosphate. The salt between a (poly)phosphoric acid and piperazine can be obtained by the following method. Piperazine pyrophosphate, for example, can be easily obtained by causing piperazine and pyrophosphoric acid to react with each other in water or methanolic water and collecting a sparingly water-soluble precipitate. The piperazine polyphosphate for use in the invention can be a salt formed between piperazine and a polyphosphoric acid mixture containing orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, and other polyphosphoric acids. The composition of the starting polyphosphoric acid mixture is not particularly limited.
[0042] Component (B) may be a mixture of two or more compounds.
[0043] The amount of component (A) is preferably 5 to 60 parts, more preferably 10 to 30 parts, even more preferably 12 to 20 parts by mass per 100 parts by mass of the TPU elastomer. The amount of component (B) is preferably 10 to 90 parts, more preferably 15 to 45 parts, even more preferably 18 to 30 parts, by mass per 100 parts by mass of the TPU elastomer.
[0044] In order to achieve a high fire resistance without affecting the physical properties of the TPU elastomer, the sum of the amounts of components (A) and (B) is preferably from 15 to 65 parts, more preferably 25 to 55 parts, still more preferably 30 to 50 parts by mass per 100 parts by mass of the TPU elastomer. If the sum is less than 15 parts, the TPU elastomer composition may fail to exhibit sufficient fire resistance. If the sum exceeds 65 parts, the resin's intrinsic physical properties may be reduced.
The mass ratio of the constitution of component (A) to component (B), (A)/(B), is preferably 20/80 to 50/50, more preferably 30/70 to 50/50.
[0046] Component (C) used in the invention will be described.
[0047] Component (C) used in the invention is silicon dioxide. When added, it is effective in preventing dripping.
[0048] Silicon dioxide can have any shape, powdery or granular. The type of silicon dioxide is not particularly limited and can be either natural silica or synthetic silica; it can be either crystalline silica or amorphous silica; it can be any one of dry silica, fumigated silica, fused silica, and wet silica; and it can have pores on the inside (porous silica or porous silica) or be porousless (non-porous silica).
[0049] Silicon dioxide is preferably finely divided particles, and an average primary particle size thereof is preferably 0.005 to 30 µm, more preferably 0.1 to 10 µm, even more preferably 0.5 to 5 µm. Silica with an average primary particle size greater than 12 µm can reduce the inherent physical properties of the resin. The average primary particle size can be determined using, for example, a laser diffraction/scatter particle size distribution analyzer.
[0050] Silicon dioxide can be surface treated with a silane coupling agent, a surface treating agent or the like.
Commercially available silicon dioxide products usable include Aerosil from Nippon Aerosil Co., Ltd.; Reosil and Tokusil from Tokuyama Corp.; Carplex of Shionogi & Co., Ltd.; Sylcia from Fuji Silysia Chemical, Ltd.; and Mizukasil of Mizusawa Industrial Chemicals, Ltd.
[0052] The amount of silicon dioxide as component (C) is preferably 0.1 to 10.0 parts, more preferably 0.5 to 5.0 parts, even more preferably 1.5 to 3.0 parts, by mass per 100 parts by mass of TPU elastomer. When the amount is less than 0.1 parts, silicon dioxide may fail to exhibit an anti-drip effect. When added in an amount greater than 10.0 parts, silicon dioxide can reduce the physical properties of the resin.
[0053] It is preferred that the fire resistant TPU elastomer composition of the invention still contains (D) zinc oxide. Zinc oxide can be surface treated. Commercially available zinc oxide products can be used, including JIS class 1 zinc oxide available from Mitsui Mining and Smelting Co. Ltd., partially coated zinc oxide available from Mitsui Mining and Smelting Co. Ltd., Nanofine 50 (oxide of ultra-fine zinc oxide 0.02 µm mean particle diameter) from Sakai Chemical Industries Ltd., and Nanofine K (ultra-fine zinc oxide 0.02 µm mean particle diameter coated with zinc silicate) from Sakai Chemical Industries Ltd .
[0054] The amount of zinc oxide as component (D) is preferably 0.1 to 10 parts, more preferably 0.5 to 5.0 parts, even more preferably 1.0 to 3.0 parts, by mass per 100 bulk parts of the TPU elastomer composition.
[0055] The fire resistant TPU elastomer composition of the invention may further contain a silicone oil to reduce secondary agglomeration and improve water resistance. Examples of suitable silicone oils include dimethyl silicone oil (polysiloxane having methyl as all side groups and both end groups), methyl phenyl silicone oil (polysiloxane having phenyl as part of side groups), methyl hydrogen silicone oil (polysiloxane having hydrogen in part of the side chains), and copolymers of these siloxanes. Modified silicone oils can be used, which are obtained by introducing an organic group apart from the side and/or end chains of the polysiloxanes described above, such as amine, epoxy, alicyclic epoxy, carboxyl, carbinol, mercapto modified silicone oils , polyether, long chain alkyl, fluoroalkyl, higher fatty acid ester, higher fatty acid amide, silanol, diol, phenol and/or aralkyl.
[0056] Examples of usable silicone oils include KF-96, KF-965, and KF-968, all from Shin-Etsu Chemical Co., Ltd. (as dimethyl silicone oil); KF-99 and KF-9901, both from Shin-Etsu Chemical, HMS-151, HMS-071, HMS-301, and DMS-H21, all from Gelest (as methyl hydrogen silicone oil or a silicone oil having a structure of methyl hydrogen polysiloxane); KF-50, KF-53, KF-54, and KF-56, all from Shin-Etsu Chemical (as methyl phenyl silicone oil); X-22-343, X-22-2000, KF-101, KF-102, and KF-1001, all from Shin-Etsu Chemical (as epoxy-modified silicone oils); X-22-3701E from Shin-Etsu Chemical (as carboxyl-modified silicone oils); X-22-4039 and X-22-4015, both from Shin-Etsu Chemical (as carbinol-modified silicone oils); and KF-393 from Shin-Etsu Chemical (as amine-modified silicone oils).
[0057] The fire resistant TPU elastomer composition of the invention may further contain a silane coupling agent. A silane coupling agent is a compound having an organic functional group and a hydrolyzable group and is represented by, for example, general formula: A-(CH2)k-Si(OR)3, where A is an organic functional group , k is a number from 1 to 3, and R is methyl or ethyl. The organic group like A can be epoxy, vinyl, methacryl, amino or mercapto. For use in the invention, a silane coupling agent with an epoxy group is preferred.
[0058] The fire resistant TPU elastomer composition of the invention may further contain a polyhydric alcohol compound as a fire resistance aid. A polyhydric alcohol compound is a compound having a plurality of hydroxyl groups, such as pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1,3,5-tris(2-hydroxyethyl) isocyanurate (THEIC), polyethylene glycol, glycerol, diglycerol, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose and lactose. Preferred among them are at least one compound selected from the group consisting of pentaerythritol and pentaerythritol condensates such as pentaerythritol, dipentaerythritol, tripentaerythritol and polypentaerythritol. Dipentaerythritol and other pentaerythritol condensates are more preferred. Dipentaerythritol is more preferred. THEIC and sorbitol are also preferably used.
[0059] The pentaerythritol condensate may be a mixture of pentaerythritol and a pentaerythritol condensate, which will hereinafter be called a mixture of (poly)pentaerythritol. When a degree of condensation of pentaerythritol is represented by "n", the (poly)pentaerythritol mixture is characterized by containing a total of 5% to 40% by mass of pentaerythritol (n=1) and its smaller condensates (n=2 and 3) with respect to the total amount of the (poly)pentaerythritol mixture. Note that the total amount of pentaerythritol (n=1), lower pentaerythritol condensates (n=2 and 3) and upper pentaerythritol condensates (n>4) is taken as 100% by mass.
[0060] The total content of pentaerythritol (n=1) and its lower condensates (n=2 and 3) is preferably 10 to 30% by mass with respect to the total amount of the (poly)pentaerythritol mixture aiming at fire resistance. It is more preferred that the content of pentaerythritol (n=1) is from 0 to 10% by mass and that the total content of pentaerythritol (n=1) and its lower condensates (n=2 and 3) is from 5 to 30% in large scale. It is even more preferred that the pentaerythritol content (n=1) is from 0 to 5% by mass and that the total content of pentaerythritol (n=1) and lower pentaerythritol condensates (n=2 and 3) is from 10 to 30% by mass.
[0061] Pentaerythritol and its condensates include compounds represented by the general formula (4):
[Chemical formula 4] where t is an integer of 1 or greater.
[0062] The (poly)pentaerythritol mixture may contain a pentaerythritol condensate obtained by forming an ether bond in the molecule of a pentaerythritol condensate having formula (4), a pentaerythritol condensate in which intermediate methylol group(s) ) is/are ether linked with other molecule(s), a pentaerythritol condensate in which molecules are linked in a meshed fashion, and/or a pentaerythritol condensate in which molecules are further linked to increase in size and form structures of macrocyclic ethers at various sites.
[0063] The (poly)pentaerythritol mixture is not particularly limited and can be produced by any known method. For example, the (poly)pentaerythritol mixture can be prepared by subjecting pentaerythritol and/or a pentaerythritol condensate to a dehydration and condensation reaction under heating either directly or in the presence of an appropriate catalyst and solvent.
[0064] Examples of the catalyst used for preparing the (poly)pentaerythritol mixture include inorganic acids and organic acids which are generally used in a dehydration and condensation reaction of an alcohol. Examples of the inorganic acids include mineral acids such as phosphoric acid and sulfuric acid; acid salts of these mineral acids; and solid acid catalysts such as clay minerals (eg, montmorillonite), silica-alumina, and zeolite. Examples of the organic acids include formic acid and p-toluenesulfonic acid.
[0065] The amount of catalyst to be used is not particularly limited. When a water-soluble acid catalyst is used, it can be used in an amount that maintains the pH of the reaction system during the reaction to less than 7, preferably 5 or less. When a solid acid catalyst is used, it is generally used in an amount of 0.15 to 100% by mass with respect to the amount of pentaerythritol.
[0066] Examples of the solvent used for preparing the (poly)pentaerythritol mixture include hydrocarbons such as benzene, xylene, decalin and tetralin; ethers such as dioxane, tetrahydrofuran, ethyl ether, anisole, phenyl ether, diglyme, tetraglyme, and 18-crown-6; ketones such as methyl acetate, ethyl butyrate, methyl benzoate, and y-butyrolactone; N-substituted amides such as N-methylpyrrolidin-one, N,N-dimethylacetamide, N-methylpiperidone, and hexamethylphosphoric triamide; tertiary amines such as N,N-diethylaniline, N-methylmorpholine, pyridine and quinoline; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; urea derivatives such as 1,3-dimethyl-2-imidazolidinone; phosphine oxides such as tributylphosphine oxide; and silicone oils. These solvents can be dehydrated or hydrated.
[0067] The temperature of dehydration and condensation reaction under heating in the preparation of the (poly)pentaerythritol mixture is generally about 100 to 280°C, more preferably 150 to 240°C. When the reaction temperature is less than 100°C, the reaction progress may be slow, while when the reaction temperature is greater than 280°C, it may be difficult to control the condensation reaction.
[0068] The amount of polyhydric alcohol, if added, is preferably 0.01 to 10.0 parts by mass, more preferably 1.0 to 7.0 parts by mass, even more preferably 1.5 to 3.0 parts by mass mass, per 100 parts by mass of the TPU elastomer.
[0069] The fire resistant TPU elastomer composition of the invention may preferably contain a lubricant as needed. Examples of lubricants include pure hydrocarbon lubricants such as liquid paraffins, natural paraffins, microwaxes, synthetic paraffins, low molecular weight polyethylenes, and polyethylene waxes; halogenated hydrocarbon lubricants; fatty acid lubricants such as higher fatty acids and oxy-fatty acids; fatty acid amide lubricants such as fatty acid amides and bis-fatty acid amides; ester lubricants such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids (eg, glycerides), polyglycol fatty acid esters, and fatty alcohol esters of fatty acids (ester waxes); metal soaps; fatty alcohols; polyhydric alcohols; polyglycols; polyglycerols; partial esters of fatty acids and polyhydric alcohols; partial esters of fatty acids and polyglycol or polyglycerol; silicone oils; and mineral oils.
[0070] The amount of lubricant to be added is preferably 0.01 to 5 parts, more preferably 0.3 to 2 parts by mass per 100 parts by mass of the TPU elastomer.
[0071] When necessary, the fire resistant TPU elastomer composition of the invention may contain one or more halogen-free organic or inorganic fire resistance agents or fire resistance agent auxiliaries in an amount that does not harm the effects of invention. Examples of usable fire resistance agents and fire resistance agent auxiliaries include triazine ring containing compounds, metal hydroxides, phosphoric ester fire resistance agents, condensed phosphoric ester fire resistance agents, fire resistance agents of phosphate, inorganic phosphorus fire resistance agents, dialkyl phosphinates, silicone fire resistance agents, metal oxides oxides, boric acid compounds, thermally expandable graphite, other auxiliary inorganic fire resistance agents, and others organic fire resistance agents.
[0072] Examples of the triazine ring-containing compounds include melamine, amelin, benzoguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimethylamine, trimethylene dimethylamine, tetramethylene dimethylamine, hexamethylene dimethylamine, and 1,3- hexylene dimethylamine.
[0073] Examples of metal hydroxides include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide and KISUMA 5a® (magnesium hydroxide from Kyowa Chemical Industry Co., Ltd.).
[0074] Examples of phosphoric ester fire resistance agents include trimethyl phosphate, triethyl phosphate, tributyl phosphate, taxoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, trixylenyl phosphate, octyldiphenyl phosphate, xylenyldiphenyl phosphate, triisopropylphenyl phosphate, 2-ethylhexyldiphenyl phosphate, t-butylphenyldiphenyl phosphate, bis(t-butylphenyl)phenyl phosphate, tris(t-butylphenyl)phosphate, isopropylphenyldiphenyl phosphate , bis(isopropylphenyl)diphenyl phosphate and tris(isopropylphenyl) phosphate.
[0075] Examples of the condensed phosphoric ester fire resistance agents include 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylenyl phosphate), and bis(diphenyl phosphate) bisphenol A.
[0076] Examples of inorganic phosphorus fire resistance agents include red phosphorus.
[0077] Examples of the dialkyl phosphinates include diethyl aluminum phosphinate and diethyl zinc phosphinate.
[0078] Examples of the other inorganic fire resistance agent auxiliaries include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and hydrotalcite; and its surface treated products. Various commercially available products of these fire resistance agent auxiliaries can be used, including TIPAQUE R-680R (titanium oxide from Ishihara Sangyo Kaisha, Ltd.), KYOWA MAG 150R (magnesium oxide from Kyowa Chemical Industry Co., Ltd.). ), DHT-4A (hydrotalcite from Kyowa Chemical Industry Co., Ltd.), and ALCAMIZER 4R (zinc-modified hydrotalcite from Kyowa Chemical Industry Co., Ltd.).
[0079] If desired, the fire resistant TPU elastomer composition of the invention may contain a phenol antioxidant, a phosphorus antioxidant, a thioether antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, an anti- deterioration and the like.
[0080] Examples of the phenol antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate. distearyl, bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide] of 1,6-hexamethylene, 4,4'-thiobis(6-tert-butyl-m-cresol), 2, 2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-m-cresol ), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2- methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris isocyanurate (3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2-tert -butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methyl benzyl)phenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid methyl]methane, bis[ thiodiethylene glycol (3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene glycol ester bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid], bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5) terephthalate -methylbenzyl)phenyl], 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate], 3,9-bis[1,1-dimethyl-2-{( 3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and bis[(3-tert-butyl-4-hydroxy-5 - triethylene glycol methylphenyl)propionate].
[0081] The phenol antioxidant is added in an amount of preferably 0.001 to 10 parts, more preferably 0.05 to 5 parts by mass per 100 parts by mass of the TPU elastomer.
[0082] Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2, 6-di-tert-butyl-4-methylphenyl)pentaerythritol, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, tetra(tridecyl) diphosphite isopropylidenediphenol, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-methyl) triphosphite hydroxy-5-tert-butylphenyl)butane, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, 2-phosphite, 2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl, 2,2'-methylenebis(4,6-tert-butyl) phosphite enyl)octadecyl, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl) fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1]) ,3,2]dioxafosfepin-6-yl)oxy]ethyl)amine, 2-ethyl-2-butylpropylene glycol phosphite and 2,4,6-tri-tert-butylphenol and tris(2,4-di-phosphite) tert-butylphenyl).
[0083] The amount of phosphorus antioxidant to be added is preferably 0.001 to 10 parts, more preferably 0.05 to 5 parts, by mass 100 parts by mass of the TPU elastomer.
Examples of the thioether antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and a pentaerythritol tetra(β-alkylthiopropionate).
[0085] The amount of the thioether antioxidant to be added is preferably 0.001 to 10 parts, more preferably 0.05 to 5 parts by mass per 100 parts by mass of the TPU elastomer.
[0086] Examples of the UV absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy- 4-methoxybenzophenone); 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole , 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy -3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), 2-(2'-hydroxy-3'-tert-butyl-5'- carboxyphenyl)benzotriazole; benzoates such as phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di- tert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates such as α-cyano-β,β-ethyl diphenylacrylate and methyl 2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and triaryl triazines, such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)- 4,6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine.
[0087] The amount of UV absorber to be added is preferably 0.001 to 30 parts, more preferably 0.05 to 10 parts by mass per 100 parts by mass of the TPU elastomer.
[0088] Examples of the hindered amine light stabilizer include hindered amine compounds such as 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-stearate pipyridyl, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl sebacate), bis(1,2,2,6,6) sebacate - tetramethyl-4-piperidyl), bis(1-oxtoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,3,4-tetrakis(2,2,6,6-butanetetracarboxylate) -tetramethyl-4-piperidyl), 1,2,3,4-tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl), 1,2,3,4-butanetetracarboxylate bis(2 ) bis(1,2,2,6,6-pentamethyl-4-piperidyl)di(tridecyl) 1,2,3,4-butanetetracarboxylate Bis(1,2,2,4,4-pentamethyl-4-piperidyl)malonate, 2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-polycondensates) hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-di polycondensates chloro-6-mofolino-s-triazine, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-5 tert-octylamino-s-triazine polycondensates , 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]- 1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino )-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11 -tris[2,4-bis(N-butyl-N- (2,2,6,6- tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, and 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6) -pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane.
[0089] The amount of the hindered amine light stabilizer to be added is preferably 0.001 to 30 parts, more preferably 0.05 to 10 parts by mass, per 100 parts by mass of the TPU elastomer.
[0090] Examples of the anti-decay agent include naphthylamines, diphenylamines, p-phenyldiamines, quinolines, hydroquinone derivatives, monophenols, thiobisphenols, hindered phenols, phosphite esters. The amount of the anti-decay agent to be added is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the TPU elastomer.
[0091] The fire resistant TPU elastomer composition of the present invention may optionally contain a reinforcing material in an amount that does not detract from the effects of the invention. The reinforcing material may have a fibrous, plate, granular, powder form, as is common for application to synthetic resins. Specific examples of useful reinforcement materials include inorganic fibrous reinforcement materials such as glass fibers, asbestos fibers, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, whisker silicon, wollastonite, sepiolite, asbestos, slag fiber, zonolite, ellestatite, gypsum fiber, silica fiber, silica alumina fibers, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber; organic fibrous reinforcement materials such as polyester fibers, nylon fibers, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie, cotton, jute, hemp, sisal, flax flax, linen, silk, manila fiber, sugar cane, wood pulp, waste paper, used paper, and wool; and reinforcing materials in plate or granular form, such as glass flakes, non-swellable mica, graphite, thin sheet metal, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, silicic acid powder, feldspar powder, potassium titanate, shirasu flask, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, gypsum, novaculite, dawsonite, and white clay. The reinforcing material may have been coated or sized with a thermoplastic resin such as an ethylene-vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or it may have been treated with a coupling agent such as an aminosilane or an epoxysilane.
[0092] The fire resistant TPU elastomer composition of the invention may optionally contain a sheet silicate in an amount that does not affect the effects of the invention. Examples of suitable sheet silicates include smectite clay minerals such as montmorillonite, saponite, hectorite, beidelite, stynsite and nontronite, vermiculite, halloysite, swollen mica, and talc. The sheet silicate can have an organic cation, a quaternary ammonium cation, or a phosphonium cation pre-intercalated between the layers thereof.
[0093] The fire resistant TPU elastomer composition of the invention may optionally contain a crystal nucleating agent in an amount that does not affect the effects of the invention. Any crystal nucleating agents commonly used for polymers can be used as appropriate. In the present invention, an inorganic crystal nucleating agent or an organic crystal nucleating agent can be used.
[0094] Examples of the inorganic crystal nucleating agent include kaolinite, synthetic mica, clay, zeolite, graphite, carbon black, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, neodymium oxide, and metal salts of phenyl phosphonate and the like. The inorganic crystal nucleating agent can be modified with an organic substance so as to have improved dispersibility of the composition.
[0095] Examples of the organic nucleating agent include metal salts of organic carboxylic acids such as sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, stearate calcium, magnesium stearate, barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, β-naphthalate sodium, and sodium cyclohexanecarboxylate; organic sulfonic acid salts such as sodium p-toluenesulfonate and sodium sulfoisophthalate; carboxylic amides such as stearamide, ethylenebislauramide, palmitamide, hydroxystearamide, erucamide, and tris(tert-butyramide) trimesic acid; benzylidenesorbitol and its derivatives; metal salts of phosphorus compounds, such as sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate; and 2,2-methylbis(4,6-di-tert-butylphenyl) sodium.
[0096] The fire resistant TPU elastomer composition of the invention may optionally contain a plasticizer in an amount that does not impair the effects of the invention. Any plasticizers that are commonly used for polymers can be used as appropriate, including polyester plasticizers, glycerol plasticizers, polycarboxylic ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.
[0097] Examples of polyester plasticizers include those formed from an acid component such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, or rosin pitch and a diol component such as propylene glycol, 1, 3-butanediol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, or diethylene glycol; and compounds of a hydroxycarboxylic acid such as polycaprolactone. These polyesters can be terminated with a monofunctional carboxylic acid or a monofunctional alcohol, or they may be terminated with an epoxy compound.
[0098] Examples of the glycerol plasticizers include glycerol monoacetomonolaurate, glycerol diacetomonolaurate, glycerol monoacetomonostearate, glycerol diacetomonooleate, and glycerol monoacetomonomontanate.
[0099] Examples of the polycarboxylic ester plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate and butyl benzyl phthalate; trimellitate, such as tributyl trimellitate, trioctyl trimellitate, and trihexyl trimellitate; adipates such as diisodecyl adipate, n-octyl n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, and benzyl butyl diglycol adipate; citrates such as acetyl triethyl citrate and acetyl tributyl citrate; azelates such as di-2-ethylhexyl azelate; and sebacates such as dibutyl sebacate and di-2-ethylhexyl sebacate.
[00100] Examples of polyalkylene glycol plasticizers include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, a block and/or random copolymer of poly(ethylene oxide - propylene oxide), polytetramethylene glycol, ethylene oxide addition polymers of bisphenols, propylene oxide addition polymers of bisphenols, and tetrahydrofuran oxide addition polymers of bisphenols; and its terminal block compounds, such as terminal epoxy modified compounds, terminal ester modified compounds, and terminal ether modified compounds.
[00101] The term "epoxy plasticizer" generally refers to epoxy triglycerides composed of epoxy alkyl stearate and soybean oil. So-called epoxy resins prepared primarily from bisphenol A and epichlorohydrin are also usable.
[00102] Examples of other usable plasticizers include benzoates of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, and triethylene glycol di-2-ethylbutyrate; fatty acid amides such as stearamide; aliphatic carboxylic esters such as butyl oleate; oxyacid esters such as methyl acetylricinolate and butyl acetylricinolate; pentaerythritol, sorbitols, polyacrylates and paraffins. The plasticizers described above can be used either individually or in combination of two or more of them.
[00103] The fire resistant TPU elastomer composition of the invention may optionally contain an acrylic processing aid in an amount that does not detract from the effects of the invention. The acrylic processing aid is exemplified by a homopolymer of one (meth)acrylic ester or a copolymer of two or more (meth)acrylic esters.
[00104] The fire resistant TPU elastomer composition of the invention may contain an anti-drip agent in an amount that does not adversely affect the effects of the invention. It should be noted, however, that it is not advisable to use a fluorine-containing anti-drip agent from the standpoint of being halogen free and also because the physical properties of the TPU elastomer, particularly elongation, could be reduced. It is particularly unfavorable to use polytetrafluoroethylene.
[00105] Examples of the fluorine-containing anti-drip agent include fluorocarbon resins such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene, and alkali metal or alkaline earth metal salts of perfluoroalkanesulfonic acids such as sodium perfluoromethanesulfonate, perfluoro-n-butanesulfonate potassium, potassium perfluoro-t-butane sulfonate, sodium perfluorooctane sulfonate, and calcium perfluoro-2-ethylhexane sulfonate.
[00106] If desired, the fire resistant TPU elastomer composition of the present invention may contain additives commonly used for synthetic resins, provided that the effects of the invention are not impaired. Usable additives include crosslinking agents, antistatics, metal soaps, fillers, anti-fog agents, anti-scattering agents, surface treatment agents, fluorescent agents, antifungals, bactericides, foaming agents, metal inactivators, separating agents, pigments, processing aids and the like.
[00107] When the fire resistant TPU composition of the present invention contains components other than TPU and components (A) to (D) (excluding resins other than TPU elastomer), the quantities of the optional components are not particularly limited, since that the effects of the invention are not impaired. However, it is preferable that the total amount of the optional components is not more than 100 parts, more preferably not more than 50 parts, by mass, per 100 parts by mass of the TPU elastomer.
[00108] The fire resistant TPU elastomer composition of the invention may contain a different synthetic resin than the TPU elastomer as a resin component. Synthetic resins usable include thermoplastic resins, including polyolefin and olefin copolymers, for example α-olefin polymers such as polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, crosslinked polyethylene, molecular weight polyethylene ultra-high, polybutene-1, and poly-3-methylpentene, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, and ethylene-propylene copolymers; halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymers, vinyl-ethylene chloride copolymers, vinyl chloride copolymers- vinylidene chloride, vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, vinyl chloride-acrylic ester copolymers, vinyl chloride-maleic ester copolymers, and vinyl chloride-cyclohexylmaleimide copolymers; petroleum resins, coumarone resins, polystyrene, polyvinyl acetate, acrylic resins, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; aromatic polyester resins, including polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, and polycyclohexanedimethylene terephthalate, polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate, and linear polyester resins such as polytetramethylene terephthalate; degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, and poly(2-oxetanone); polyamide resins such as polyphenylene oxide, polycaprolactam, and polyhexamethylene adipamide; polycarbonate, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, cellulose resins; and polyblends of these thermoplastic resins. Also included in usable synthetic resins are thermoforming resins, such as phenol resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins, fluororesins, silicone resins, polyether sulfone silicone rubber, polysulfone, polyphenylene ether, polyether ketone , polyether ether ketone, and liquid crystal polymers. Also usable are isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, and silicone rubber. Additional examples of the synthetic resin include thermoplastic olefin elastomers, thermoplastic styrene elastomers, thermoplastic polyester elastomers, thermoplastic nitrile elastomers, thermoplastic nylon elastomers, thermoplastic vinyl chloride elastomers, and thermoplastic elastomers.
[00109] These synthetic resins can be used either individually or in combination of two or more of them. They can be used in polymer alloy form.
[00110] The synthetic resins described above can be used without considering the molecular weight, degree of polymerization, density, softening point, insoluble content in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and ratio of the composition of monomers, catalyst type for polymerization (eg Ziegler type or metallocene type), and the like.
[00111] Preferred of these synthetic resins described are ethylene polymers such as high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE); and ethylene copolymers such as ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-acrylic acid copolymers, and ethylene-methacrylic acid copolymers.
[00112] When using resins other than TPU elastomer, the amount of the other resins is not particularly limited, but it is preferably not greater than 100 parts, more preferably not greater than 50 parts, by mass per 100 parts by mass of the TPU elastomer.
[00113] In preparing the fire resistant TPU elastomer composition of the invention, the time to mix the TPU elastomer with the essential components (A), (B) and (C) and the optional component (D) is not particularly limited. For example, any two or more of components (A) to (D) can be premixed, and the resulting premix can be added to the TPU elastomer, or components (A) to (D) can be added separately to the TPU elastomer. In the first case, each component to be pre-mixed can be pre-ground, or grinding can follow pre-mix. The same mixing mode described above applies to resin other than TPU elastomer and other optional components.
[00114] The fire resistant TPU elastomer composition of the invention can be molded to give molded articles with excellent fire resistance. The fire resistant TPU elastomer composition of the invention can be molded by any known molding techniques, such as extrusion, calendering, injection, lamination, compression, and blown film extrusion, to give articles of various shapes, such as sheets, sheets , films, or any other irregular shapes.
[00115] The fire resistant TPU elastomer composition of the invention and molded articles thereof find wide applications in various industrial fields, including electrical and electronic, communications, agriculture, forestry, fishing, mining, construction, food, fiber, clothing, medicine, coal, petroleum, rubber, leather, automobiles, precision equipment, wood, building materials, civil engineering, furniture, printing, musical instruments, and so on. Specifically, applications include stationery and AO equipment such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, copiers, fax machines, ECRs (electronic cash registers), calculators, electronic diaries, cards, media, and writing tools; household appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, and kotatsu; audio and video equipment such as TV sets, VTRs, video cameras, radio cassette recorders, tape recorders, mini-discs, CD players, speakers and liquid crystal displays; electrical and electronic components, such as connectors, relays, capacitors, switches, printed circuit boards, coil bodies, semiconductor sealants, LED sealants, electrical wires, cables, transformers, bypass coils, switchboards, and clocks; housings (frames, boxes, covers and enclosures) and parts of communication equipment and OA equipment; and automotive parts for interiors and exteriors.
[00116] The fire resistant TPU elastomer composition of the invention and its molded products are also useful in various applications, including materials for gas (gasoline) vehicles, hybrid vehicles, electric vehicles, train cars, boats, ships, aircraft , buildings and houses, such as seats (stuffing and upholstery), straps, roof covering, convertible tops, arm rests, door moldings, tailgate trays, mats, mats, sun visors, wheel covers, mattress protectors, air bags, insulating materials, auxiliary gripping cables, auxiliary straps, wire covering, electrical insulators, paints, coatings, overlays, floors, inner corner moldings, carpets, wallpaper, wall covering, exterior cladding, interior cladding, ceilings, decks, walls, pillars, floor boards, fences, frames and moldings, window and door profiles, ceiling tiles, siding boards, terraces, balconies, soundproof boards, soundproof boards. thermal slippers and window frames; civil engineering materials; and household items and sports equipment, such as clothing, curtains, sheets, particleboard, fiber boards, carpets and rugs, doormats, sheets, buckets, hoses, containers, cups, bags, boxes, goggles, skis, rackets, tents and musical instruments. EXAMPLES
[00117] The invention will now be illustrated in greater detail with reference to the Examples, but the invention is not considered limited thereto. Unless otherwise noted, all parts are expressed by mass, and the composition ratios in Table 1 are given in terms of parts by mass. Examples 1 to 5 and Comparative Example 1 to 5
[00118] One hundred parts of a TPU elastomer (Resamine P-2283 from Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was mixed with 0.1 parts of calcium stearate as a lubricant, 0.1 parts of tetrakis[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)5 methyl propionate]methane as a phenol antioxidant, 0.1 part of tris(2,4-di-t-butylphenyl) phosphite as an antioxidant of phosphorus, 0.3 parts of glycerol monostearate as a lubricant, and components shown in Table 1 below. The resulting mixture was extruded at 200°C to obtain granules. The beads were injection molded at 190°C to obtain specimens 127 mm long, 12.7 mm wide, and 1.6 mm thick. In Example 1 and Comparative Example 1, specimens 100 mm long, 100 mm wide, and 2 mm thick were also prepared.
[00119] Components (A) and (B) in Table 1 were thus prepared. Preparation examples Component (A): Melamine Pyrophosphate
[00120] Melamine pyrophosphate was prepared by the reaction between pyrophosphoric acid and melamine in a molar ratio of 1:2. Preparation Examples 2 Component (B): Piperazine Pyrophosphate
[00121] Piperazine pyrophosphate was prepared by the reaction between pyrophosphoric acid and piperazine in a molar ratio of 1:1.
[00122] The specimens prepared in Examples 1 to 5 and Comparative Example 1 to 5 were evaluated for fire resistance by the UL-94 test according to the procedure described below. Results obtained are in Table 1. UL-94 Flammability Test Method:
[00123] Each sample (127 mm long, 12.7 mm wide, 1.6 mm thick) was held with the long axis vertical. A flame from a burner was applied to the lower end of the sample for 10 seconds and removed, and the duration of the flame was recorded. Once the specimen had stopped burning, the flame was reapplied for an additional 10 seconds, and the flame duration was measured in the same way as for the first flame application. Ignition of the cotton layer placed below the specimen by any droplets of ignited particles was also observed.
[00124] The duration of the flame after each flame application and ignition of the cotton layer has been interpreted in flammability classification UL-94. The V-0 rating is the lowest flammability. The V-1 rating is less fire resistance, and the V-2 rating is even less fire resistance. A specimen whose test results were not interpreted in any of these classifications was classified as "NR".
[00125] The 100 mm long, 100 mm wide, and 2 mm thick specimens prepared in Example 1 and Comparative Example 1 were tested using a cone calorimeter (CONE III, from Toyo Seiki Co., Ltd. ) according to ISO5660 to measure the heat release rate (HRR) in the radiant flux described below. The total heat released (THR) (MJ/m2), peak heat release rate (PHRR)(kW/m2), and PHRR duration (s) are shown in Table 1 (radiant flux: 50 kW/m2) .
[00126] After the cone test, the specimens were photographed to see the formation of a swollen surface layer. The maximum thickness of the swollen surface layer was measured. Photographs of the specimens from Example 1 and Comparative Example 1 are shown in Figures 1 and 2, respectively. The maximum thickness of the swollen surface layer is shown in Table 1. Table 1

[00127] As can be seen from Table 1, all specimens from Examples 1 to 5 were classified as V-0 in the UL94 flammability test. In contrast, the specimens of Comparative Examples 1 to 5 dripped burning particles that initiated the cotton burning and were classified as V-2. The specimen from Example 1 was superior to Comparative Example 1 in fire resistance in terms of total heat released and peak heat release rate.
[00128] As shown in Table 1 and Figure 1, the specimen from Example 1 formed a sufficiently swollen surface layer, proving to be able to retard the diffusion of a decomposition product and heat transfer. In contrast, as shown in Table 1 and Figure 2, the formation of a swollen surface layer is insufficient in Comparative Example 1, proving to be inferior in delaying the diffusion of a decomposition product and heat transfer.

权利要求:
Claims (6)
[0001]
1. Fire resistant thermoplastic polyurethane elastomer composition, characterized in that it comprises a thermoplastic polyurethane elastomer, (A) a (poly)phosphate compound represented by the general formula (1):
[0002]
2. Fire-resistant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that it further comprises zinc oxide (D).
[0003]
3. Fire resistant thermoplastic polyurethane elastomer composition according to claim 1 or 2, characterized in that component (A) is melamine pyrophosphate represented by the general formula (1) wherein n is 2, p is 2, and X1 is melamine which is a compound having the general formula (2), wherein Z1 and Z2 are each -NH2.
[0004]
4. A fire-resistant thermoplastic polyurethane elastomer composition according to any one of claims 1 to 3, characterized in that component (B) is a piperazine polyphosphate represented by the general formula (3), wherein q is 1, and Y1 is piperazine.
[0005]
5. Fire resistant thermoplastic polyurethane elastomer composition according to claim 4, characterized by the fact that piperazine polyphosphate is piperazine pyrophosphate.
[0006]
6. Molded article, characterized in that it is obtained from the composition of fire-resistant thermoplastic polyurethane elastomer, according to any one of claims 1 to 5.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

IT1201097B|1983-05-18|1989-01-27|Montedison Spa|FLAME RESISTANT POLYMERIC COMPOSITIONS|

---

JPH09221567A|1996-02-13|1997-08-26|Chisso Corp|Flame-retardant polyolefin resin composition|

---

JP2001049053A|1999-08-06|2001-02-20|Dainippon Ink & Chem Inc|Resin composition and its molded product|

---

JP3637277B2|2000-03-21|2005-04-13|大塚化学ホールディングス株式会社|Flame retardant, flame retardant resin composition, molded product, and electronic component|

---

JP2002234118A|2000-12-05|2002-08-20|Dainippon Ink & Chem Inc|Laminated sheet having fire retardancy and flat cable|

---

US6710108B2|2001-08-30|2004-03-23|General Electric Company|Flame-retardant polyester composition, method for the preparation thereof, and articles derived therefrom|

---

DE10218911A1|2002-04-26|2003-11-06|Basf Ag|Foil flat conductors comprising thermoplastic polyurethanes|

---

AU2003244110A1|2002-06-24|2004-01-06|Asahi Denka Co., Ltd.|Flame retarder composition and flame retardant resin composition containing the composition|

---

JP4526255B2|2003-10-16|2010-08-18|株式会社Ａｄｅｋａ|Method for producing high purity piperazine pyrophosphate|

---

EP1745114A4|2003-11-29|2011-11-30|Kasowski Robert Valentine|Protective barrier composition comprising reaction of phosphorous acid with amines applied to a substrate|

---

JP5543343B2|2008-06-16|2014-07-09|株式会社Ａｄｅｋａ|Non-halogen flame retardant synthetic resin composition|

---

JP5344742B2|2008-08-01|2013-11-20|株式会社Ａｄｅｋａ|Flame retardant thermoplastic resin composition|

---

US7829614B2|2008-12-30|2010-11-09|Sabic Innovative Plastics Ip B.V.|Reinforced polyester compositions, methods of manufacture, and articles thereof|

---

US8138244B2|2008-12-30|2012-03-20|Sabic Innovative Plastics Ip B.V.|Reinforced polyester compositions, method of manufacture, and articles thereof|

---

JP5363195B2|2009-05-25|2013-12-11|株式会社Ａｄｅｋａ|Flame retardant synthetic resin composition with excellent moldability|

---

BR112012003075B1|2009-08-10|2019-11-19|Union Carbide Chem Plastic|coated wire and method for making a coated wire|

---

JP5556183B2|2009-10-06|2014-07-23|住友電気工業株式会社|Flame retardant resin composition and insulated wire, flat cable, molded product using the same|

---

US20120238664A1|2009-12-11|2012-09-20|Wilson Xiao Wei Yan|Thermoplastic Polymer Blends Comprising Crosslinked Polar Olefin Polymers in a Thermoplastic Polyurethane Matrix|

---

US8859643B2|2010-06-07|2014-10-14|Basf Se|Encapsulated flame retardants for polymers|

---

JP2012052092A|2010-08-06|2012-03-15|Fire Proof Technology Co Ltd|Flame retardant resin composition and method for producing the same|

---

KR20130127493A|2010-12-17|2013-11-22|다우 글로벌 테크놀로지스 엘엘씨|Halogen-free, flame retardant composition for wire and cable applications|

---

PL2681267T3|2011-03-02|2015-06-30|Huntsman Int Llc|Polyurethane flame retardant formulation|

---

CN102303770B|2011-05-20|2015-08-19|上海永利带业股份有限公司|Flame retardant thermoplastic polyurethane elastomer light-type conveyer belt|

---

EP2933311B1|2012-12-17|2019-06-19|Adeka Corporation|Flame retardant composition and flame-retardant synthetic resin composition|

---

CN103333364B|2013-06-17|2015-08-19|青岛科技大学|Complex intumescent flame retardant and the application in polypropylene flame redardant and urethane thereof|JP6739862B2|2015-11-27|2020-08-12|株式会社Adeka|Flame-retardant resin composition|

---

CN106905686A|2015-12-22|2017-06-30|万华化学集团股份有限公司|A kind of halogen-free fire retardation thermoplastic polyurethane elastic composition and its product and halogen-free flame retardants bag|

---

US10738159B2|2016-03-14|2020-08-11|Adeka Corporation|Flame retardant thermoplastic polyurethane resin composition|

---

CN106279634A|2016-09-06|2017-01-04|南京大学|A kind of high-strength anti-flaming hard polyaminoester insulation material for building and preparation method thereof|

---

CN108385399A|2017-03-24|2018-08-10|合肥云都棉花有限公司|A kind of arc protection raincoat fabric and preparation method thereof|

---

JP6279789B1|2017-03-31|2018-02-14|株式会社Adeka|Flame retardant composition and flame retardant synthetic resin composition containing the same|

---

KR101950594B1|2017-07-12|2019-02-20|박희대|Thermoplastic polyurethane sheet composition apply to bag or purse|

---

US10522269B1|2017-08-11|2019-12-31|Nexans|Cable sheath containing a polymer blend of polyvinylbutyral and thermoplastic polyurethane|

---

US10214645B1|2017-08-11|2019-02-26|Nexans|Polymer blend for cable jackets|

---

CN107481789A|2017-09-20|2017-12-15|泰州日顺电器发展有限公司|A kind of high fire-retardance is anti-to hydrolyze extraordinary spiral wires and its manufacture method|

---

CN109705564A|2017-10-25|2019-05-03|江苏瑞凌新能源科技有限公司|A kind of ultra-toughness automobile parts plastic formula|

---

CN109705563B|2017-10-26|2021-03-16|中国石油化工股份有限公司|Flame retardant thermoplastic polyurethane composition and expanded beads thereof|

---

CN108550413B|2018-03-27|2019-09-06|青岛胶州电缆有限公司|The soft electric control cable of flame-proof crosslinked polyethylene insulation shielding and its production technology|

---

CN108897109A|2018-07-20|2018-11-27|江苏亨通光电股份有限公司|Low-smoke non-halogen flame-retardant air-blowing micro-pipe|

---

CN110802852B|2019-11-15|2021-03-19|南京荣仕景复合材料有限公司|Pultrusion process and product of continuous glass fiber reinforced polyurethane microcellular foam profile and pultrusion system thereof|

---

CN111518382A|2020-06-01|2020-08-11|六安市叶集区聚诚高分子材料有限公司|High-temperature-resistant and aging-resistant thermoplastic elastomer material|

---

CN111736363A|2020-06-22|2020-10-02|温州市展视眼镜有限公司|Spectacle leg support frame and processing technology thereof|

---

KR102214921B1|2020-10-27|2021-02-15|케이엘건설 주식회사|Polyurethane seal composition with root isolation performance|

---

KR102341612B1|2021-05-14|2021-12-20|이종욱|Fire retarded wall guard using thermo plastic elastomer material and manufacturing method thereof|

法律状态:
2018-05-29| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-01-07| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-09-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/02/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2014091229A|JP2015042730A|2014-04-25|2014-04-25|Flame retardant thermoplastic polyurethane elastomer composition|

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JP2014-091229|2014-04-25|

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PCT/JP2015/054409|WO2015162982A1|2014-04-25|2015-02-18|Fire-resistant thermoplastic polyurethane elastomer composition|

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