Patent Application
20210246373
The present invention relates to a polyphosphate amine salt composition, a polyphosphate amine salt flame retardant composition, a flame-retardant synthetic resin composition containing the same, and a molded article thereof. More particularly, the present invention relates to: a polyphosphate amine salt composition which does not foam during processing, has excellent workability and excellent weather resistance, and can impart excellent flame retardancy to synthetic resins; a polyphosphate amine salt flame retardant composition; a flame-retardant synthetic resin composition containing the same; and a molded article thereof.
Synthetic resins are, because of their excellent chemical and mechanical properties, widely used in building materials, automobile components, packaging materials, agricultural materials, housing materials of home electric appliances, toys, and the like. However, many of the synthetic resins are flammable; therefore, depending on the application, flame-proofing of such synthetic resins is indispensable. As a flame-proofing method, it is widely known to use one or a combination of halogen-based flame retardants, inorganic phosphorus-based flame retardants such as red phosphorus, organophosphorus-based flame retardants typified by triaryl phosphate compounds, metal hydroxides, and flame retardant aids such as antimony oxide and melamine compounds.
Halogen-based flame retardants, however, have a problem of generating a toxic gas upon combustion. Thus, attempts have been made to use a phosphorus-based flame retardant that does not cause such a problem. Particularly, phosphate-based flame retardants composed of ammonium polyphosphate or a salt formed by polyphosphoric acid and an amine have been used because of their excellent flame retardancy. For example, Patent Document 1 proposes a flame-retardant synthetic resin composition that contains ammonium polyphosphate. In addition, Patent Document 2 proposes a flame-retardant synthetic resin composition that contains melamine polyphosphate and piperazine polyphosphate. Further, Patent Document 3 proposes the use of a phosphate-based flame retardant, such as ammonium polyphosphate or melamine pyrophosphate, in combination with a hydroxy group-containing compound or a partial ester thereof.
[Patent Document 1] JPH08-176343A
[Patent Document 2] JP2003-026935A
[Patent Document 3] JP2002-146119A
Problems to be Solved by the Invention
However, the polyphosphate-based flame retardants proposed in Patent Documents 1 and 2 have a problem in workability in that they cause molding defects such as foaming, although they have excellent flame retardancy. In addition, molded articles obtained using these flame retardants have a problem in terms of weather resistance. On the other hand, the flame retardant proposed in Patent Document 3 can inhibit foaming. Nevertheless, the inhibition of foaming is not sufficient, and improvement of weather resistance is not considered at all in Patent Document 3.
In view of the above, an object of the present invention is to provide: a polyphosphate amine salt composition which does not foam during processing, has excellent workability and excellent weather resistance, and can impart excellent flame retardancy to synthetic resins; a polyphosphate amine salt flame retardant composition; a flame-retardant synthetic resin composition containing the same; and a molded article thereof.
The present inventors intensively studied to solve the above-described problems and consequently directed their focus to the amount of orthophosphate amine salt contained in a polyphosphate amine salt composition used as a flame retardant, thereby completing the present invention.
That is, the polyphosphate amine salt composition of the present invention is a polyphosphate amine salt composition containing an orthophosphate amine salt and a polyphosphate amine salt, the composition being characterized by containing the orthophosphate amine salt in an amount of 0.1 to 6.0% by mass.
An amine in the polyphosphate amine salt composition of the present invention is preferably melamine or piperazine, more preferably a mixture of a polyphosphate amine salt composition (A) in which the amine is melamine and a polyphosphate amine salt composition (B) in which the amine is piperazine. Further, in the polyphosphate amine salt composition of the present invention, the content ratio of the polyphosphate amine salt composition (A) and the polyphosphate amine salt composition (B), (A)/(B), is preferably in a range of 20/80 to 80/20 in terms of mass ratio.
The polyphosphate amine salt flame retardant composition of the present invention is characterized by containing the polyphosphate amine salt composition of the present invention.
The flame-retardant synthetic resin composition of the present invention is characterized in that the polyphosphate amine salt flame retardant composition of the present invention is incorporated into a synthetic resin.
In the flame-retardant synthetic resin composition of the present invention, the synthetic resin is preferably a polyolefin-based resin.
The molded article of the present invention is characterized by being obtained from the flame-retardant synthetic resin composition of the present invention.
According to the present invention, the following can be provided: a polyphosphate amine salt composition which does not foam during processing, has excellent workability and excellent weather resistance, and can impart excellent flame retardancy to synthetic resins; a polyphosphate amine salt flame retardant composition; a flame-retardant synthetic resin composition containing the same; and a molded article thereof.
Embodiments of the present invention will now be described in detail.
First, the polyphosphate amine salt composition of the present invention will be described. The polyphosphate amine salt composition of the present invention is a composition which contains at least one orthophosphate amine salt and at least one polyphosphate amine salt. In the polyphosphate amine salt composition of the present invention, the term “phosphate” as in “polyphosphate amine salt” is a general term for orthophosphate, pyrophosphate, and polyphosphate.
In the polyphosphate amine salt composition of the present invention, the term “phosphate amine salt” encompasses an orthophosphate amine salt and a polyphosphate amine salt. The orthophosphate amine salt is a salt formed by orthophosphoric acid and an amine, and the polyphosphate amine salt is a salt formed by polyphosphoric acid and an amine. Examples of the polyphosphoric acid in the polyphosphate amine salt include condensates of orthophosphoric acid (H3PO4) condensates (Hn+2PnO3n+1, n represents a positive integer of 2 or larger) and, in the polyphosphate amine salt composition of the present invention, all of pyrophosphoric acid (H4P2O7) in which two orthophosphoric acid molecules are condensed, triphosphoric acid (H5P3O10) in which three orthophosphoric acid molecules are condensed, and orthophosphoric acid condensates in which four or more orthophosphoric acid molecules are condensed correspond to the polyphosphoric acid, and any one or a mixture thereof may be used. Further, metaphosphoric acid ((HPO3)m, m in represents a positive integer) is also included in the polyphosphoric acid. These polyphosphoric acids mainly have a linear structure; however, they may contain a branched structure or have a cyclic structure. In the polyphosphate amine salt composition of the present invention, the polyphosphate amine salt may be constituted by any one of, or a mixture of two or more of these polyphosphoric acids. The polyphosphate amine salt is a salt formed by polyphosphoric acid and an amine and may be a normal salt, an acidic salt, or a basic salt. Further, the amine of the polyphosphate amine salt may be a single amine, a mixture of two or more amines, or a double salt.
Examples of the amine in the phosphate amine salt include ammonia (in the polyphosphate amine salt composition of the present invention, ammonia is also regarded as an amine), alkylamines aromatic amines, and heterocyclic amines. The amine may contain a hydroxy group. The polyphosphate amine salt may be constituted by any one of, or two or more of these amines.
Examples of the alkylamines include monoalkylamines represented by R1NH2, dialkylamines represented by R1R2NH, trialkylamines represented by R1R2R3N, and diamines represented by [R4R5N(CH2)tNR6R7]. R1, R2 and R3, which are optionally the same or different, each represent a linear or bunched alkyl group having 1 to 8 carbon atoms; R4, R5, R6 and R7, which are optionally the same or different, each represent a hydrogen atom or a linear or branched alkyl group having, 1 to 8 carbon atoms; and t represents a positive integer, which is preferably 1 to 20.
Examples of the monoalkylamines include methylamine, ethylamine, propylamine, and isopropylamine. Examples of the dialkylamines include dimethylamine, methylethylamine, diethylamine, dipropylamine, methylpropylamine, and ethylpropylamine. Examples of the trialkylamines include trimethylamine, dimethylethylamine dimethylpropylamine, methyldiethylamine, methyldipropylamine, triethylamine, and tripropylamine.
Examples of the diamines represented by [R4R5N(CH2)tNR6R7] include N,N,N′,N′-tetramethyldiaminomethane, ethylenediamine, N,N′-dimethylethylenediamine, N,N′-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N,N′,N′-tetramethylethenediamine, N,N,N′,N′-diethylethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane.
Examples of the aromatic amines include aromatic monoamines, aromatic diamines and aromatic triamines. Examples of the aromatic monoamines include aniline. Examples of the aromatic diamines include 1,2-diaminobenzene, 1,4-diaminobenzene, and 1,3-diaminobenzene. Examples of the aromatic triamines include 1,3,5-triaminobenzene.
Examples of the heterocyclic amines include those having 2 to 14 carbon atoms, which contain at least one nitrogen atom and/or at least one selected from a sulfur atom and an oxygen atom. Examples of such heterocyclic amines include aliphatic heterocyclic amines having 2 to 7 carbon atoms, 5-membered aromatic heterocyclic amines having 2 to 4 carbon atoms, 6-membered aromatic heterocyclic amines having 2 to 5 carbon atoms, and polycyclic aromatic heterocyclic amines having 5 to 12 carbon atoms.
Examples of the aliphatic heterocyclic compounds having 2 to 7 carbon atoms include piperidine, piperazine, morpholine, quinuclidine, pyrrolidine, azetidine, azetidin-2-one, and aziridine, among which compounds having a 4- to 9-membered ring are preferred, and compounds having a 6-membered ring are particularly preferred.
Examples of the 5-membered aromatic heterocyclic compounds having 2 to 4 carbon atoms include pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, and isothiazole.
Examples of the 6-membered aromatic heterocyclic amines having 2 to 5 carbon atoms include melamine, pyridine, pyrimidine, pyridazine, pyrazine, and 1,2,3-triazine.
Examples of the polycyclic aromatic heterocyclic amines having 5 to 12 carbon atoms include quinoline, isoquinoline, quinazoline, phthalazine, indole, benzimidazole, purine, acridine and phenothiazine.
Specific examples of amines other than the above-described ones include: heterocyclic amines, such as 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; and diamines, such as trans-2,5-dimethylpiperazine, 1,4-bis(2-aminoethyl)piperazine, and 1,4-bis(3-aminopropyl)piperazine.
When these amines have a hydroxy group, examples of such amines include monoalkylamines represented by R1NH2, dialkylamines represented by R1R2NH, and trialkylamines represented by R1R2R3N, in which one or more hydrogen atoms in each alkyl is/are substituted with a hydroxy group(s), such as methanolamine, ethanolamine, dimethanolamine, diethanolamine, trimethanolamine, and triethanolamine.
The amine in the phosphate amine salt is preferably at least one selected from the group consisting of ammonia, alkylamines, aromatic amines, heterocyclic amines, ethanolamine, diethanolamine, and diethylenetriamine, more preferably at least one selected from the group consisting of ammonia, diethylamine, ethanolamine, diethanolamine, aniline, melamine, morpholine, ethylenediamine, piperazine, 1,2-diaminobenzene, 1,4-diaminobenzene, diethylenetriamine, methylamine, ethylamine, and dimethylamine. From the standpoints of workability, weather resistance and flame retardancy, the amine is still more preferably melamine or piperazine.
In the polyphosphate amine salt composition of the present invention, the polyphosphate amine salt can be any combination of one or more of the above-described polyphosphoric acids and one or more of the above-described amines. For example, when the polyphosphoric acid is a combination of pyrophosphoric acid and triphosphoric acid and the amine is a combination of piperazine and melamine, examples of the polyphosphate amine salt include piperazine pyrophosphate, piperazine triphosphate, melamine pyrophosphate, and melamine triphosphate, as well as double salts formed by pyrophosphoric acid, piperazine and melamine, and double salts formed by triphosphoric acid, piperazine and melamine.
In the polyphosphate amine salt composition of the present invention, the amine of the orthophosphate amine salt and the amine of the polyphosphate amine salt may be the same; however, a polyphosphate amine salt composition which is obtained by preparing the polyphosphate amine salt composition of the present invention that is composed of a single amine, further preparing the polyphosphate amine salt composition of the present invention that is composed of other amine, and subsequently mixing these compositions is also preferred from the standpoints of workability weather resistance and flame retardancy.
In the polyphosphate amine salt composition of the present invention, the amine is preferably melamine or piperazine from the standpoints of workability, weather resistance and flame retardancy, and the polyphosphate amine salt is preferably a melamine polyphosphate or a piperazine polyphosphate, more preferably a melamine pyrophosphate or a piperazine pyrophosphate, from the standpoints of workability, weather resistance and flame retardancy. Further, from the standpoints of workability, weather resistance and flame retardancy, the melamine pyrophosphate is preferably dimelamine pyrophosphate in which the molar ratio of pyrophosphoric acid and melamine is 1:2. Moreover, from the standpoints of workability, weather resistance and flame retardancy, the piperazine pyrophosphate is preferably monopiperazine pyrophosphate in which the molar ratio of pyrophosphoric acid and piperazine is 1:1. From the standpoints of workability and weather resistance as well as flame retardancy in particular, it is preferred to use a melamine polyphosphate and a piperazine polyphosphate in combination, and it is more preferred to use a melamine pyrophosphate and a piperazine pyrophosphate in combination.
When the amine in the polyphosphate amine salt composition is melamine, as for the molar ratio of phosphoric acid and melamine in melamine phosphate, from the standpoints of workability, weather resistance and flame retardancy, the ratio of melamine is preferably 0.8 to 1.2 mol, more preferably 0.9 to 1.1 mol, with respect to 1 mol of phosphorus atom of phosphoric acid.
When the amine in the polyphosphate amine salt composition is piperazine, as for the molar ratio of phosphoric acid and piperazine in piperazine phosphate, from the standpoints of inhibition of corrosion of a processing machine as well as weather resistance and flame retardancy, the ratio of piperazine is preferably 0.4 to 0.6 mol, more preferably 0.45 to 0.55 mol, with respect to 1 mol of phosphorus atom of phosphoric acid.
The polyphosphate amine salt composition of the present invention contains 0.1 to 6.0% by mass of the orthophosphate amine salt when a total content of the orthophosphate amine salt and the polyphosphate amine salt is 100% by mass. When the content of the orthophosphate amine salt is higher than 6.0% by mass, the composition foams during processing and the workability is thus poor, while when the content of the orthophosphate amine salt is less than 0.1% by mass, the weather resistance is poor. From the standpoints of workability, weather resistance and flame retardancy, the content of the orthophosphate amine salt is preferably 0.2 to 4.0% by mass, more preferably 0.3 to 3.0% by mass, still more preferably 0.5 to 2.0% by mass.
Further, from the standpoints of workability, weather resistance and flame retardancy, the content of the polyphosphate amine salt in a total amount of the orthophosphate amine salt and the polyphosphate amine salt is preferably not less than 80.0% by mass, more preferably not less than 90% by mass, still more preferably not less than 95.0% by mass, yet still more preferably not less than 98.0% by mass.
In the polyphosphate amine salt composition of the present invention, the content of the orthophosphate amine salt and that of the polyphosphate amine salt are preferably determined by an analysis method using ion chromatography.
In the polyphosphate amine salt composition of the present invention, a phosphate amine salt obtained by neutralizing phosphoric acid and an amine can be used; however, from the standpoints of workability and weather resistance, it is preferred to use a polyphosphate amine salt obtained by a dehydration-condensation reaction of an amine salt of orthophosphoric acid with heating. From the standpoints of workability and weather resistance, it is more preferred to use a polyphosphate amine salt obtained by a dehydration-condensation reaction of an amine salt of orthophosphoric acid with heating that is performed in a solid-phase state, and the temperature of the dehydration-condensation reaction performed in a solid-phase state is preferably 120 to 350° C., more preferably 150 to 300° C., still more preferably 160 to 280° C. The dehydration-condensation reaction may be performed with adjustment of the reaction temperature, the reaction time and the like while analyzing, by ion chromatography, the residual amount of the amine salt of orthophosphoric acid used as a raw material and the amount of the polyphosphate amine salt being generated as a product.
In the case of a melamine polyphosphate, from the standpoints of workability, weather resistance and flame retardancy, a melamine salt of orthophosphoric acid that is used as a raw material is preferably monomelamine orthophosphate constituted by 1 mol of orthophosphoric acid and 1 mol of melamine. Further, in the case of a piperazine polyphosphate, from the standpoints of workability, weather resistance and flame retardancy, a piperazine salt of orthophosphoric acid that is used as a raw material is preferably monopiperazine diorthophosphate constituted by 2 mol of orthophosphoric acid and 1 mol of piperazine.
In the polyphosphate amine salt composition of the present invention, from the standpoints of workability, weather resistance and flame retardancy, it is preferred that the polyphosphate amine salt be a melamine polyphosphate and the orthophosphate amine salt be a melamine orthophosphate (preferably monomelamine orthophosphate).
In the polyphosphate amine salt composition of the present invention, from the standpoints of workability, weather resistance and flame retardancy, it is also preferred that the polyphosphate amine salt be a piperazine polyphosphate and the orthophosphate amine salt be a piperazine orthophosphate (preferably monopiperazine diorthophosphate).
Furthermore, in the polyphosphate amine salt composition of the present invention, from the standpoints of workability and weather resistance as well as flame retardancy in particular, it is more preferred to use a combination of a polyphosphate amine salt composition (A) in which the amine is melamine and a polyphosphate amine salt composition (B) in which the amine is piperazine. In this case, from the standpoints of workability and weather resistance as well as flame retardancy, the content ratio (mass basis) of the polyphosphate amine salt composition (A) in which the amine is melamine and the polyphosphate amine salt composition (B) in which the amine is piperazine, (A)/(B), is preferably 20/80 to 80/20, more preferably 20/80 to 50/50, still more preferably 30/70 to 50/50, yet still more preferably 35/65 to 45/55.
Next, the polyphosphate amine salt flame retardant composition of the present invention will be described. The polyphosphate amine salt flame retardant composition of the present invention contains the polyphosphate amine salt composition of the present invention. The polyphosphate amine salt composition of the present invention is suitably used in a flame retardant, particularly a flame retardant of a synthetic resin, and is used as a polyphosphate amine salt flange retardant composition. When used as a polyphosphate amine salt flame retardant composition, the flame retardant composition may contain one or more kinds of the polyphosphate amine salt composition of the present invention.
In the polyphosphate amine salt flame retardant composition of the present invention, from the standpoints of workability, weather resistance and flame retardancy, the content of the polyphosphate amine salt composition of the present invention is preferably 10% by mass to 100% by mass, more preferably 20% by mass to 100% by mass.
From the standpoints of workability, weather resistance and flame retardancy, the polyphosphate amine salt flame retardant composition of the present invention preferably contains a polyphosphate amine salt composition (A) (hereinafter, referred to as “composition (A)”) in which the amine is melamine and which is composed of a melamine polyphosphate and a melamine orthophosphate.
Further, from the standpoints of workability, weather resistance and flame retardancy, the polyphosphate amine salt flame retardant composition of the present invention preferably contains a polyphosphate amine salt composition (B) (hereinafter, referred to as “composition (B)”) in which the amine is piperazine and which is composed of a piperazine polyphosphate and a piperazine orthophosphate.
Moreover, from the standpoints of workability and weather resistance as well as flame retardancy in particular, the polyphosphate amine salt flange retardant composition of the present invention preferably contains the composition (A) and the composition (B). From the standpoints of workability and weather resistance as well as flame retardancy in particular, the content ratio (mass basis) of the composition (A) and the composition (B), (A)/(B), is preferably 20/80 to 80/20, more preferably 20/80 to 50/50, still more preferably 30/70 to 50/50, yet still more preferably 35/65 to 45/55.
In the polyphosphate amine salt flame retardant composition of the present invention, a metal oxide that serves as a flame retardant aid may be incorporated as required within a range that does not impair the effects of the present invention. Examples of the metal oxide include zinc oxide, titanium oxide, magnesium oxide, and silicon oxide, among which zinc oxide is preferred. These metal oxides may be surface-treated as well.
As zinc oxide, a commercially available product can be used, and examples thereof include Zinc Oxide Type 1 (manufactured by Mitsui Mining and Smelting Co., Ltd.), partially coated-type zinc oxide (manufactured by Mitsui Mining and Smelting, Co., Ltd.), NANOFINE 50 (ultrafine zinc oxide particles having an average particle size of 0.02 μm, manufactured by Sakai Chemical Industry Co., Ltd.), and NANOFINE K (zinc silicate-coated ultrafine zinc oxide particles having an average particle size of 0.02 μm; manufactured by Sakai Chemical Industry Co., Ltd.). When a metal oxide is incorporated, the content thereof is, from the standpoint of flame retardancy, preferably 0.01 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, still more preferably 1.0 to 7.5 parts by mass, with respect to a total of 100 parts by mass of the phosphate amine salts (orthophosphate amine salt and polyphosphate amine salt) contained in the polyphosphate amine salt flame retardant composition. When the content of the metal oxide is less than 0.01 parts by mass, the metal oxide does not exert a sufficient effect as a flame retardant aid, while when the content of the metal oxide is higher than 10 parts by mass, the metal oxide may cause deterioration of resin properties.
In addition, in the polyphosphate amine salt flame retardant composition of the present invention, an anti-drip agent may be incorporated as required within a range that does not impair the effects of the present invention. Examples of the anti-drip agent include fluorine-based anti-drip agents, silicone rubbers, and layered silicates.
The anti-drip agent is particularly preferably a fluorine-based anti-drip agent, and specific examples thereof include: fluorocarbon resins, such as polytetrafluoroethylenes, polyvinylidene fluorides, and polyhexafluoropropylenes; and alkali metal salts of perfluoroalkane sulfonic acids and alkaline earth metal salts of perfluoroalkane sulfonic acids, such as sodium perfluoromethane sulfonate, potassium perfluoro-n-butane sulfonate, potassium perfluoro-t-butane sulfonate, sodium perfluorooctane sulfonate, and calcium perfluoro-2-ethylhexane sulfonate. Among these anti-drip agents, a polytetrafluoroethylene is most preferred because of its drip-inhibiting property.
Examples of the layered silicates include: smectite-type clay minerals, such as montmorillonite, saponite, hectorite, beidellite, stevensite and nontronite; vermiculite; halloysite, swellable mica; and talc, and those in which organic cations, quaternary ammonium cations or phosphonium cations are intercalated between layers can also be used.
When an anti-drip agent is incorporated, the content thereof is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 5 parts by mass, still more preferably 0.05 to 3 parts by mass, yet still more preferably 0.1 to 1 part by mass, with respect to a total of 100 parts by mass of the phosphate amine salts (orthophosphate amine salt and polyphosphate amine salt) contained in the polyphosphate amine salt flame retardant composition. When the content of the anti-drip agent is less than 0.005 parts by mass, a sufficient drip-inhibiting effect is not attained, while when the content of the anti-drip agent is higher than 5 parts by mass, the anti-drip agent may cause deterioration of resin properties.
Further, in the polyphosphate amine salt flame retardant composition of the present invention, for the purposes of inhibiting secondary aggregation during blending and improving the water resistance, a silicone oil may be incorporated as required within a range that does not impair the effects of the present invention. Examples of the silicone oil include: dimethyl silicone oils in which the side chains and terminals of polysiloxane are all methyl groups; methylphenyl silicone oils in which some of the side chains of polysiloxane are phenyl groups; methyl hydrogen silicone oils in which some of the side chains of polysiloxane are hydrogen atoms; and copolymers of these silicone oils. In addition, modified silicone oils in which organic groups are introduced to some of the side chains and/or terminals of the above-described silicone oils, for example, amine-modified, epoxy-modified, alicyclic epoxy-modified, carboxyl-modified, carbinol-modified, mercapto-modified, polyether-modified, long-chain alkyl-modified, fluoroalkyl-modified, higher fatty acid ester-modified, higher fatty acid amide-modified, silanol-modified, diol-modified, phenol-modified and/or aralkyl-modified silicone oils, can also be used.
Specific examples of the silicone oil include: dimethyl silicone oils, such as KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-965 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-968 (manufactured by Shin-Etsu Chemical Co., Ltd.); methyl hydrogen silicone oils or silicone oils having a methyl hydrogen polysiloxane structure, such as KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd.), HMS-151 (manufactured by Gelest Inc.), HMS-071 (manufactured by Gelest Inc.), HMS-301 (manufactured by Gelest Inc.), and DMS-H21 (manufactured by Gelest Inc.); methylphenyl silicone oils, such as KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-53 (manufactured by Shin-Etsu Chemical Co. Ltd.), KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-56 (manufactured by Shin-Etsu Chemical Co., Ltd.); epoxy-modified products, such as X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-2000 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-102 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-1001 (manufactured by Shin-Etsu Chemical Co., Ltd.); carboxyl-modified products, such as X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd.); carbinol-modified products, such as X-22-4039 (manufactured by Shin-Etsu Chemical Co., Ltd.) and X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.); and amine-modified products, such as KF-393 (manufactured by Shin-Etsu Chemical Co., Ltd.).
When a silicone oil is incorporated, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, still more preferably 0.5 to 3 parts by mass, with respect to a total of 100 parts by mass of the phosphate amine salts (orthophosphate amine salt and polyphosphate amine salt) contained in the polyphosphate amine salt flame retardant composition. When the content of the silicone oil is less than 0.01 parts by mass, the inhibition of secondary aggregation and the improvement of water resistance may be insufficient, while when the content of the silicone oil is higher than 10 parts by mass, the silicone oil may cause deterioration of resin properties.
Still further, in the polyphosphate amine salt flame retardant composition of the present invention, for the purposes of inhibiting aggregation of flame retardant powder to improve the storage stability and imparting water resistance and heat resistance, a silane coupling agent may be incorporated as required within a range that does not impair the effects of the present invention.
Examples of the silane coupling agent include: alkenyl group-containing silane coupling agents, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, vinylmethyldimethoxysilane, octenyltrimethoxysilane, allyltrimethoxysilane and p-styryltrimethoxysilane; acryl group-containing silane coupling agents, such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; methacryl group-containing silane coupling agents, such as 3-methacryloxyproplymethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and methacryloxyoctyltrimethoxysilane; epoxy group-containing silane coupling agents, such as 2-(3,4-epoxycyclohexy)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and glycidoxyoctyltrimethoxysilane; amino group-containing silane coupling agents, such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N′-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and a hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate group-containing silane coupling agents, such as tris(trimethoxysilylpropyl)isocyanurate; mercapto group-containing silane coupling agents, such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane; ureido group-containing silane coupling agents, such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane; sulfide group-containing silane coupling agents, such as bis(triethoxysilylpropyl)tetrasulfide; thioester group-containing silane coupling agents, such as 3-octanoylthio-1-propyltriethoxysilane; and isocyanate group-containing silane coupling agents, such as 3-isocyanate propyltriethoxysilane and 3-isocyanate propyltrimethoxysilane. Among these silane coupling agents from the standpoints of inhibiting aggregation of flame retardant powder to improve the storage stability and imparting water resistance and heat resistance, epoxy group-containing same coupling agents are preferred.
As the silane coupling agent, a commercially available product can be used, and examples thereof include: vinyltrimethoxysilane, such as KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd., A-171 manufactured by Momentive Performance Materials Japan LLC, Z-6300 manufactured by Dow Corning Toray Co., Ltd., GENIOSIL XL10 manufactured by Wacker Asahikasei Silicone Co., Ltd., and SILA-ACE S210 manufactured by Nichibi Trading Co., Ltd.; vinyltriethoxysilane, such as KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd., A-151 manufactured by Momentive Performance Materials Japan LLC, Z-6519 manufactured by Dow Corning Toray Co., Ltd., GENIOSIL GF56 manufactured by Wacker Asahikasei Silicone Co., Ltd., and SILA-ACE S220 manufactured by Nichibi Trading Co., Ltd.; vinyltriacetoxysilane, such as GENIOSIL GF62 manufactured by Wacker Asahikasei Silicone Co., Ltd.; vinyltris(2-methoxyethoxy)silane, such as A-172 manufactured by Momentive Performance Materials Japan LLC; vinylmethyldimethoxysilane, such as A-2171 manufactured by Momentive Performance Materials Japan LLC and GENIOSIL XL12 manufactured by Wacker Asahikasei Silicone Co., Ltd.; octenyltrimethoxysilane, such as KBM-1083 manufactured by Shin-Etsu Chemical Co., Ltd.; allyltrimethoxysilane, such as Z-6825 manufactured by Dow Corning Toray Co., Ltd.; p-stryltrimethoxysilane, such as KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd.; 3-acryloxypropyltrimethoxysilane, such as KBM-5103; 3-methacryloxypropylmethyldimethoxysilane, such as KBM-502 manufactured by Shin-Etsu Chemical Co., Ltd., and Z-6033 manufactured by Dow Corning Toray Co., Ltd.; 3-methacryloxypropyltrimethoxysilane, such as KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd., A-174 manufactured by Momentive Performance Materials Japan LLC, Z-6030 manufactured by Dow Corning Toray Co., Ltd., GENIOSIL GF31 manufactured by Wacker Asahikasei Silicone Co., Ltd., and SILA-ACE S710 manufactured by Nichibi Trading Co., Ltd.; 3-methacryloxypropylmethyldiethoxysilane, such as KBE-502 manufactured by Shin-Etsu Chemical Co., Ltd.; 3-methacryloxypropyltriethoxysilane such as KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd., and Y-9936 manufactured by Momentive Performance Materials Japan LLC; methacryloxyoctyltrimethoxysilane, such as KBM-5803 manufactured by Shin-Etsu Chemical Co., Ltd.;
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, such as KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd., A-186 manufactured by Momentive Performance Materials Japan LLC, Z-6043 manufactured by Dow Corning Toray Co., Ltd., and SILA-ACE S530 manufactured by Nichibi Trading Co., Ltd.; 3-glycidoxypropylmethyldimethoxysilane such as KBM-402 manufactured by Shin-Etsu Chemical Co., Ltd., Z-6011 manufactured by Dow Corning Toray Co., Ltd., and SILA-ACE S520 manufactured by Nichibi Trading Co., Ltd.; 3-glycidoxypropyltrimethoxysilane, such as KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd., A-187 manufactured by Momentive Performance Materials Japan LLC, Z-6040 manufactured by Dow Corning Toray Co., Ltd., GENIOSIL GF80 manufactured by Wacker Asahikasei Silicone Co., Ltd., and SILA-ACE S510 manufactured by Nichibi Trading Co., Ltd.; 3-glycidoxypropylmethyldiethoxysilane, such as KBE-402 manufactured by Shin-Etsu Chemical Co., Ltd.; 3-glycidoxypropyltriethoxysilane, such as KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd., A-1871 manufactured by Momentive Performance Materials Japan LLC, and GENIOSIL GF82 manufactured by Wacker Asahikasei Silicone Co., Ltd.; glycidoxyoctyltrimethoxysilane, such as KBM-4803 manufactured by Shin-Etsu Chemical Co., Ltd.; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, such as KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd., A-2120 manufactured by Momentive Performance Materials Japan LLC, GENIOSIL GF-95 manufactured by Wacker Asahikasei Silicone Co., Ltd., and SILA-ACE S310 manufactured by Nichibi Trading Co., Ltd.; N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, such as KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd., A-1120 manufactured by Momentive Performance Materials Japan LLC, A-1122 manufactured by Momentive Performance Materials Japan LLC, Z-6020 manufactured by Dow Corning Toray Co., Ltd., Z-6094 manufactured by Dow Corning Toray Co., Ltd., GENIOSIL GF-91 manufactured by Wacker Asahikasei Silicone Co., Ltd., and SILA-ACE S320 manufactured by Nichibi Trading Co., Ltd.; 3-aminopropyltrimethoxysilane, such as KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd., A-1110 manufactured by Momentive Performance Materials Japan LLC, Z-6610 manufactured by Dow Corning Toray Co., Ltd., and SILA-ACE S360 manufactured by Nichibi Trading Co., Ltd.; 3-aminopropyltriethoxysilane, such as KBE-903, A-1100 manufactured by Momentive Performance Materials Japan LLC, Z-6011 manufactured by Dow Corning Toray Co., Ltd., and SILA-ACE S330 manufactured by Nichibi Trading Co., Ltd.; 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, such as KBE-9103, and SILA-ACE S340 manufactured by Nichibi Trading Co., Ltd.; N-phenyl-3-aminopropyltimethoxysilane, such as KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd., Y-9669 manufactured by Momentive Performance Materials Japan LLC, and Z-6883 manufactured by Dow Corning Toray Co., Ltd.; N,N′-bis[3-(trimethoxysilyl)propyl]ethylenediamine such as SILA-ACE XS1003 manufactured by Nichibi Trading Co., Ltd.;
N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, such as KBM-575 manufactured by Shin-Etsu Chemical Co., Ltd., Z-6032 manufactured by Dow Corning Toray Co., Ltd., and SILA-ACE S350 manufactured by Nichibi Trading Co., Ltd.; tri(trimethoxysilylpropyl)isocyanurate, such as KBM-9659 manufactured by Shin-Etsu Chemical Co., Ltd.; 3-mercaptopropylmethyldimethoxysilane, such as KBM-802 manufactured by Shin-Etsu Chemical Co., Ltd., and Z-6852 manufactured by Dow Corning Toray Co., Ltd.; 3-mercaptopropyltrimethoxysilane, such as KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd., A-189 manufactured by Momentive Performance Materials Japan LLC, Z-6062 manufactured by Dow Corning Toray Co., Ltd., and SILA-ACE S810 manufactured by Nichibi Trading Co., Ltd.; 3-mercaptopropyltriethoxysilane, such as A-1891 manufactured by Momentive Performance Materials Japan LLC, and Z-6911 manufactured by Dow Corning Toray Co., Ltd.; 3-ureidopropyltriethoxysilane, such as A-1160 manufactured by Momentive Performance Materials Japan LLC; 3-ureidopropyltrialkoxysilane, such as KBE-585 manufactured by Shin-Etsu Chemical Co., Ltd.; bis(triethoxysilylpropyl)tetrasulfide, such as KBE-846 manufactured by Shin-Etsu Chemical. Co., Ltd.; 3-octanoylthio-1 -propyltriethoxysilane, such as A-LINK599 manufactured by Momentive Performance Materials Japan LLC; 3-isocyanate propyltriethoxysilane, such as KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd., and A-1310 manufactured by Momentive Performance Materials Japan LLC; and 3-isocyanate propyltrimethoxysilane, such as Y-5187 manufactured by Momentive Performance Materials Japan LLC, and GENIOSIL GF40 manufactured by Wacker Asahikasei Silicone Co., Ltd.
When a silane coupling agent is incorporated into the polyphosphate amine salt flame retardant composition of the present invention, the content thereof is preferably 0.01 to 5.0 parts by mass, more preferably 0.05 to 3.0 parts by mass, still more preferably 0.1 to 2.0 parts by mass, with respect to a total of 100 parts by mass of the phosphate amine salts (orthophosphate amine salt and polyphosphate amine salt) contained in the polyphosphate amine salt flame retardant composition.
In the polyphosphate amine salt flame retardant composition of the present invention, from the standpoints of heat resistance and weather resistance as well as reducing the risk of corrosion of a processing machine, a hydrotalcite compound may be incorporated as required within a range that does not impair the effects of the present invention. In the polyphosphate amine salt flame retardant composition of the present invention, the “hydrotalcite compound” refers to a carbonate double salt compound of magnesium and/or zinc and aluminum. The hydrotalcite compound may be a naturally-occurring or synthetic hydrotalcite. Examples of a method of synthesizing a synthetic hydrotalcite include blown methods that are described in JPS46-2280B1, JPS50-30039B1, JPS51-29129B1, JPS61-174270A and the like. In the present invention, the above-described hydrotalcites can be used without any restriction in terms of crystal structure, crystal pain system, the presence or absence of crystal water, the amount of crystal water, and the like.
The hydrotalcite compound may be treated with perchloric acid, and it is also possible to use a hydrotalcite compound dose surface is coated with, for example, a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as alkali metal oleate, a metal organic sulfonate such as alkali metal dodecylbenzenesulfonate, a higher fatty acid amide, a higher fatty acid ester, or a wax. The hydrotalcite compound is preferably a compound represented by the following Formula (I):
Mgx1Znx2Al2(OH)2(X1+X2)+4.CO3.mH2O (1)
wherein x1 and x2 each represent a number that satisfies the conditions represented by the following equations, and m represents a real number: 0≤x2/x1<10, and 2≤(x1+x2)<20.
As the hydrotalcite compound, a commercially available product can be used, and examples thereof include DHT-4 (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), MAGCELER 1 (hydrotalcite: manufactured by Kyowa Chemical Industry Co. Ltd.), ALCAMIZER 1 (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), ALCAMIZER 2 (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), ALCAMIZER 4 (ALCAMIZER P-93) (zinc-modified hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), ALCAMIZER 7 (zinc-modified hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), and ALCAMIZER 5 (perchloric acid-treated hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), among which DHT-4A (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.) is particularly preferred.
When a hydrotalcite compound is incorporated, the content thereof with respect to a total of 100 parts by mass of the phosphate amine salts (orthophosphate amine salt and polyphosphate amine salt) contained in the polyphosphate amine salt flame retardant composition is preferably 0.01 to 5 parts by mass and, from the standpoints of heat resistance and weather resistance as well as reducing the risk of corrosion of a processing machine, the content of the hydrotalcite compound is more preferably 0.05 to 4 parts by mass, still more preferably 0.1 to 2 parts by mass.
In the polyphosphate amine salt flame retardant composition of the present invention, a flame retardant aid other than the above-described metal oxides may also be incorporated as required within a range that does not impair the effects of the present invention. This flame retardant aid is, for example, a polyhydric alcohol compound.
The “polyhydric alcohol compound” refers to a compound in which plural hydroxyl groups are bound and which is added as a flame retardant aid for improving the flame retardancy. Examples of the polyhydric alcohol compound used as a flame retardant aid include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1,3,5-tris(2-hydroxyethyl)isocyanurate, polyethylene glycol, glycerin, diglycerin, mannitol, maltitol, lactitol, sorbitol, erythritol xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose, and lactose. Among these polyhydric alcohol compounds, a pentaerythritol or a pentaerythritol condensate, such as pentaerythritol, dipentaerythritol, tripentaerythritol or polypentaerythritol, is preferred, a pentaerythritol condensate is more preferred, and dipentaerythritol is particularly preferred. Further, 1,3,5-tris(2-hydroxyethyl)isocyanurate and sorbitol can be suitably used as well. The pentaerythritol condensate may be a mixture of pentaerythritol and pentaerythritol condensate.
In the polyphosphate amine salt flame retardant composition of the present invention, a lubricant may also be incorporated as required within a range that does not impair the effects of the present invention. Examples of the lubricant include: pure hydrocarbon-based lubricants, such as liquid paraffins, natural paraffins, microwaxes, synthetic paraffins, low-molecular-weight polyethylenes, and polyethylene waxes; halogenated hydrocarbon-based lubricants; fatty acid-based lubricants, such as higher fatty acids and oxy fatty acids; fatty acid amide-based lubricants, such as fatty acid amides and bis-fatty acid amides; ester-based lubricants, such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty Kids (e.g., glyceride), polyglycol esters of fatty, acids, and fatty alcohol esters of fatty acids (ester waxes); metallic soaps; fatty alcohols; polyhydric alcohols; polyglycols; polyglycerols; partial esters of fatty acids and polyhydric alcohols; partial ester-based lubricants composed of fatty acid, polyglycol and polyglycerol; silicone oils; and mineral oils. Two or more of these lubricants may be used in combination.
When a lubricant is incorporated, the content thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to a total of 100 parts by mass of the phosphate amine salts (orthophosphate amine salt and polyphosphate amine salt) contained in the polyphosphate amine salt flame retardant composition.
In the polyphosphate amine salt flame retardant composition of the present invention, one or more halogen-free organic or inorganic flame retardants or flame retardant aids may be further used as required within a range that does not impair the effects of the present invention. Examples of such flame retardants and flame retardant aids include triazine ring-containing compounds, metal hydroxides, phosphate-based flame retardants, condensed phosphate-based flame retardants, inorganic phosphorus-based flame retardants, dialkyl phosphinates, silicone-based flame retardants, metal oxides, boric acid compounds, expandable graphites, other inorganic flame retardant aids, and other organic flame retardants.
Examples of the triazine ring-containing compounds include melamine, ammeline, benzoguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, and 1,3-hexylene dimelamine.
Examples of the metal hydroxides include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and KISUMA 5A (trademark of magnesium hydroxide manufactured by Kyowa Chemical Industry Co., Ltd.).
Examples of the phosphate-based flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, trixylenyl phosphate, octyldiphenyl phosphate, xylenyldiphenyl phosphate, tris(isopropylphenyl)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.
Examples of the condensed phosphate-based flame retardants include 1,3-phenylene-bis(diphenyl phosphate), 1,3-phenylene-bis(dixylenyl phosphate), bisphenol A-bis(diphenyl phosphate), naphthalene-2,5-diyl-tetraphenyl bis(phosphate),
[1,1′-biphenyl]-4,4′-diyl-tetraphenyl bis(phosphate),
[1,1′-biphenyl]-4,4′-diyl-tetrakis(2,6-dimethylphenyl)bis(phosphate),
tetraphenyl(thiobis(4,1-phenylene))bis(phosphate), and
tetraphenyl(sulfonyl-bis(4,1-phenylene))bis(phosphate).
Examples of the inorganic phosphorus-based flame retardants include red phosphorus.
Examples of the dialkyl phosphinates include aluminum diethylphosphinate and zinc diethylphosphinate.
Examples of other inorganic flame retardant aids include inorganic compounds, such as titanium oxide, aluminum oxide, magnesium oxide, and hydrotalcite; and surface-treated products thereof. Specifically, for example, a variety of commercially available products, such as TIPAQUE R-680 (trademark of titanium oxide manufactured by Ishihara Sangyo Kaisha, Ltd.), KYOWAMAG 150 (trademark of magnesium oxide manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite, manufactured by Kyowa Chemical Industry Co., Ltd.) and ALCAMIZER 4 (trademark of zinc-modified hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd.), can be used.
In the polyphosphate amine salt flame retardant composition of the present invention, as required, a phenolic antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, an ultraviolet absorber, a hindered amine-based light stabilizer, an age inhibitor and the like may be incorporated as well. These components may be incorporated into the polyphosphate amine salt flame retardant composition of the present invention in advance, or may be incorporated into a synthetic resin at the time of blending the polyphosphate amine salt flame retardant composition with the synthetic resin. It is preferred to stabilize the synthetic resin by incorporating these components.
Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol,
2,6-diphenyl-4-octadecyloxyphenol, distearyl(3,5-di-tert-butyl-4-hydroxbenzyl)phosphonate,
1,6-hexamethylene-bis[(3,5-di-tert-butyl-4-hydroxyphenyl)promionic acid amide],
4,4′-thiobis(6-ter-butyl-cresol), 2,2′-methylene-bis(4-methyl-6-tert-butylphenol),
2,2′-methylene-bis(4-ethyl-6-tert-butylphenol), 4,4′-butylidene-bis(6-tert-butyl-m-cresol),
2,2′-ethylidene-bis(4,6-di-tert-butylphenol),
2,2′-ethylidene-bis(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(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
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-methylbenzyl)phenol,
stearyl(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid methyl]methane, thiodiethylene
glycol-bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
1,6-hexamethylene-bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester,
bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate,
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)propionyloxyl}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and triethylene
glycol-bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]. When incorporated into a synthetic resin, these phenolic antioxidants are used in an amount of preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the synthetic resin.
Examples of the phosphorus-based 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 diphosphite,
bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite,
bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetra(tridecyl)isopropylidenediphenol diphosphite, tetra(tridecyl)-4,4′-n-butylidene-bis(2-tert-butyl-5-methylphenol)diphosphite,
hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite,
tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite,
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
2,2′-methylene-bis(46-tert-butylphenyl)-2-ethylhexyl phosphite,
2,2′-methylene-bis(4,6-tert-butylphenyl)-octadecyl phosphite,
2,2′-ethylidene-bis(4,6-di-tert-butylphenyl)fluorophosphite,
tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy] ethyl)amine, and phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol. When incorporated into a synthetic resin, these phosphorus-based antioxidants are used in an amount of preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the synthetic resin.
Examples of the thioether-based antioxidant include: diallyl thiodipropionates, such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; and pentaerythritol tetra(β-alkylmercaptopropionic acid) esters. When incorporated into a synthetic resin, these thioether-based antioxidants are used in an amount of preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the synthetic resin.
Examples of the ultraviolet absorber include: 2-hydroxybenzophenones, such as
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-octoxybenzophenone, and
5,5′-methylene-bis(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′-methylene-bis(4-tert-octyl-6-(benzotriazolyl)phenol), and
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 ethyl-α-cyano-β,β-diphenylacrylate and
methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and triaryltriazines, 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. When incorporated into a synthetic resin, these ultraviolet absorbers are used in an amount of preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, with respect to 100 parts by mass of the synthetic resin.
Examples of the hindered amine-based light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate,
2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,
tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,
bis(2,2,6,6-tetramethyl-4-piperidyl)⋅bis(tridecyl)-1,2,3,4-butanetetracarboxylate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)⋅bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,
1,2,2,6,6-pentamethyl-4-piperidyl methacrylate,
poly[{6-(1,1,3,3-tramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl4-piperidyl)imino}],
1,2,3,4-butanecarboxylic acid/2,2-bis(hydroxymethyl)-1,3-propanediol/3-hydroxy-2,2-dimethylpropanal/1,2,2,6,6-pentamethyl-4-piperidinyl ester polycondensate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)=decane dioate/methyl=1,2,2,6,6-pentamethyl-4-piperidyl=sebacate mixture,
2,2,6,6-tetramethyl-4-piperidyl methacrylate,
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensate,
1,6-bis(2,2,6,6-tetramethyl-4-pipelidylamino)hexane/dibromoethane polycondensates,
1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine polycondensates,
1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-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-triazine-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-triazine-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-t-riazine-6-ylamino]undecane,
1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-ylaminol]undecane,
3,9-bis[1,1-dimethyl-2-{tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspno[5.5]undecane,
3,9-bis[1,1-dimethyl-2-{tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane,
bis(1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 2,2,6,6-tetramethyl-4-piperidyl hexadecanoate, and 2,2,6,6-tetramethyl-4-piperidyl octadecanoate. When incorporated into a synthetic resin, these hindered amine-based light stabilizers are used in an amount of preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, with respect to 100 parts by mass of the synthetic resin.
Examples of the age inhibitor include naphthylamine-based age inhibitors, diphenylamine-based age inhibitors, p-phenyldiamine-based age inhibitors, quinoline-based age inhibitors, hydroquinone derivatives, monophenol-based age inhibitors, thiobisphenol-based age inhibitors, hindered phenol-based age inhibitors, and phosphite-based age inhibitors. When incorporated into a synthetic resin, these age inhibitors are used in an amount of preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the synthetic resin.
In the polyphosphate amine salt flame retardant composition of the present invention, a reinforcing material may also be incorporated as an optional component within a range that does not impair the effects of the present invention. This component may be incorporated into a synthetic resin at the time of blending the polyphosphate amine salt flame retardant composition of the present invention with the synthetic resin. As the reinforcing material, a fiber-form, plate-form, particle-form or powder-form reinforcing material that is usually used for reinforcement of a synthetic resin can be used. Specific examples thereof include: inorganic fibrous reinforcing materials, such as glass fibers, asbestos fibers, carbon fibers, graphite fibers, metal fibers, potassium titanate whiskers, aluminum borate whiskers, magnesium-based whiskers, silicon-based whiskers, wollastonite, sepiolite, asbestos, slag fibers, zonolite, ellestadite, gypsum fibers, silica fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, and boron fibers; organic fibrous reinforcing materials, such as polyester fibers, nylon fibers, acrylic fibers, regenerated cellulose fibers, acetate fibers, kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, sugarcane, wood pulp, wastepaper, recycled wastepaper, and wool; and plate-form and particle-form reinforcing materials, such as glass flake, non-swelling mica, graphites metal foils, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine powder silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite, and white clay. These reinforcing materials may be coated or bundled with a thermoplastic resin such as an ethylene/vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane.
In the polyphosphate amine salt flame retardant composition of the present invention, a nucleating agent may be further incorporated as an optional component within a range that does not impair the effects of the present invention. As the nucleating agent, one which is generally used as a nucleating agent of a polymer can be used as appropriate and, in the present invention, any of inorganic nucleating agents and organic nucleating agents can be used. These components may be incorporated into a synthetic resin at the time of blending the polyphosphate amine salt flame retardant composition of the present invention with the synthetic resin.
Specific examples of the inorganic nucleating agents include kaolinite, synthetic mica, clay, zeolite, silica, graphite, carbon black, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, neodymium oxide, and metal salts of phenylphosphonate. These inorganic nucleating agents may be modified with an organic substance so as to improve their dispersion in the composition.
Specific examples of the organic, nucleating agents include: organic metal carboxylates 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, calcium stearate, magnesium stearate, barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, and sodium cyclohexane carboxylate, organic sulfonates, such as sodium p-toluene sulfonate and sodium sulfoisophthalate; carboxylic acid amides, such as stearic acid amide, ethylene-bis-lauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, and trimesic acid tris(t-butylamide); benzylidene sorbitol and derivatives thereof; phosphorus compound metal salts, such as sodium-2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate; and 2,2-methylbis(4,6-di-t-butylphenyl)sodium.
Further, to the polyphosphate amine salt flame retardant composition of the present invention, for the purpose of neutralizing a residual catalyst in the synthetic resin, a known neutralizer may be added as an optional component within a range that does not impair the effects of the present invention. Examples of the neutralizer include: fatty acid metal salts, such as calcium stearate, lithium stearate and sodium stearate; and fatty acid amide compounds, such as ethylene-bis(stearamide), ethylene-bis(12-hydroxystearamide) and stearic acid amide, and these neutralizers may be used in the form of a mixture.
Still further, in the polyphosphate amine salt flame retardant composition of the present invention, an acrylic processing aid may be incorporated as an optional component within a range that does not impair the effects of the present invention. As the acrylic processing aid, one obtained by polymerizing a single kind of (meth)acrylic acid ester or copolymerizing two or more kinds of (meth)acrylic acid esters can be used. This component may be incorporated into a synthetic resin at the time of blending the flame retardant composition of the present invention with the synthetic resin. Examples of the (meth)acrylic acid ester(s) to be polymerized/copolymerized include (meth)acrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, isobutyl acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and tridecyl methacrylate. Other examples include (meth)acrylic acid and hydroxy group-containing (meth)acrylates.
In the polyphosphate amine salt flame retardant composition of the present invention, a plasticizer may be further incorporated as an optional component within a range that does not impair the effects of the present invention. As the plasticizer, one which is generally used as a plasticizer of a polymer can be used as appropriate, and examples thereof include polyester-based plasticizers, glycerol-based plasticizers, polycarboxylic acid ester-based plasticizers, polyalkylene glycol-based plasticizers, ether ester-based plasticizers, and epoxy-based plasticizers. This component may also be incorporated into a synthetic resin at the time of blending the polyphosphate amine salt flame retardant composition of the present invention with the synthetic resin.
In addition to the above in the polyphosphate amine salt flange retardant composition of the present invention, an additive(s) normally used in a synthetic resin, such as a cross-linking agent, an antistatic agent, a metallic soap, a filler, an anti-fogging agent, a plate-out inhibitor, a surface treatment agent, a fluorescent agent, an antifungal agent, a disinfectant, a foaming agent, a metal inactivator, a mold release agent, a pigment and/or a processing aid other than the above-described acrylic processing aid, can be incorporated as required within a range that does not impair the effects of the present invention. These components may also be incorporated into a synthetic resin at the time of blending the polyphosphate amine salt flame retardant composition of the present invention with the synthetic resin.
In cases where two or more phosphate amine salts are used as the polyphosphate amine salt flame retardant composition of the present invention or the flame retardant composition is mixed with the above-described other components, a variety of mixing machines can be employed for mixing. The mixing may be performed with heating. Examples of the mixing machines that can be employed include a tumbler mixer, a Henschel mixer, a ribbon blender, a V-type mixer, a W-type mixer, a super mixer, and a Nauta mixer.
Next, the flame-retardant synthetic resin composition of the present invention will be described. The flame-retardant synthetic resin composition of the present invention is obtained by incorporating the polyphosphate amine salt flame retardant composition of the present invention into a synthetic resin. The polyphosphate amine salt flame retardant composition of the present invention is effective in flame-proofing of synthetic resins and preferably blended with a synthetic resin to be used as a flame-retardant synthetic resin composition. The flame-retardant synthetic resin composition of the present invention does not foam during processing and yields a molded article having excellent workability and excellent weather resistance.
Specific examples of synthetic resins to be flame-proofed by the polyphosphate amine salt flame retardant composition of the present invention include: α-olefin polymers, such as polypropylenes, high-density polyethylenes, low-density polyethylenes, linear low-density polyethylenes, cross-linked polyethylenes, ultrahigh-molecular-weight polyethylenes, polybutene-1, and poly-3-methylpentene; polyolefins and copolymers thereof, such as ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, and ethylene-propylene copolymers; halogen-containing resins, such as polyvinyl chloride, polyvinylidene chlorides, chlorinated polyethylenes, chlorinated polypropylenes, polyvinylidene fluorides, chlorinated rubbers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymers, vinyl chloride-acrylate copolymers, vinyl chloride-maleate copolymers, and vinyl chloride-cyclohexylmaleimide copolymers; petroleum resins; coumarone resins; polystyrenes; polyvinyl acetates; acrylic resins; polymethyl methacrylates; polyvinyl alcohols; polyvinyl formals, polyvinyl butyrals; aromatic polyesters, such as polyalkylene terephthalates (e.g., polyethylene terephthalate, polybutylene terephthalate, and polycyclohexane dimethylene terephthalate) and polyalkylene naphthalates (e.g., polyethylene naphthalate and polybutylene naphthalate); linear polyesters such as polytetramethylene terephthalate; degradable aliphatic polyesters, such as polyhydroxy butyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane and poly(2-oxetanone); thermoplastic resins and blends thereof, such as polyamides (e.g., polyphenylene oxide, polycaprolactam, and polyhexamethylene adipamide), polycarbonates, branched polycarbonates, polyacetals, polyphenylene sulfides, polyurethanes, and cellulose-based resins; thermosetting resins, such as phenol resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins; fluorocarbon resins; silicone resins; silicone rubber polyether sulfones; polysulfones; polyphenylene ethers; polyether ketones; polyether ether ketones; and liquid crystal polymers. Other examples include isoprene rubbers, butadiene rubbers, acrylonitrile-butadiene copolymer rubbers, styrene-butadiene copolymer rubbers, fluorine rubbers, and silicone rubbers.
Specific examples of synthetic resins to be flame-proofed further include olefin-based thermoplastic elastomers, styrene-based thermoplastic elastomers, polyester-based thermoplastic elastomers, nitrile-based thermoplastic elastomers, nylon-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, polyimide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers. These synthetic resins may be used individually, or two or more thereof may be used in combination. Further, these synthetic resins may be alloyed as well.
In the present invention, the above-described synthetic resins can be used regardless of for example, the molecular weight, the polymerization degree, the density, the softening point, the insoluble component-to-solvent ratio, the degree of stereoregularity, the presence or absence of a catalyst residue, the type and blend ratio of each material monomer, and the type of a polymerization catalyst (e.g., a Ziegler catalyst or a metallocene catalyst). Among above-described synthetic resins, polyolefin-based resins are preferred since excellent flame retardancy can be imparted thereto.
Examples of the polyolefin-based resins include: α-olefin polymers, such as polyethylenes, low-density polyethylenes, linear low-density polyethylenes, high-density polyethylenes, polypropylenes, homopolypropylenes, random copolymer polypropylenes, block copolymer polypropylenes, impact copolymer polypropylenes, high-impact copolymer polypropylenes, isotactic polypropylenes, syndiotactic polypropylenes, hemi-isotactic polypropylenes, maleic anhydride-modified polypropylenes, polybutenes, cycloolefin polymers, stereo block polypropylenes, poly-3-methyl-1-butenes, poly-3-methyl-1-pentenes, and poly-4-methyl-1-pentenes; and α-olefin copolymers, such as ethylene-propylene block or random copolymers, ethylene-methyl methacrylate copolymers, and ethylene-vinyl acetate copolymers.
In the flame-retardant synthetic resin composition of the present invention, from the standpoints of flame retardancy, workability and weather resistance, a total content of the polyphosphate amine salt flame retardant composition is preferably 10% by mass to less than 60% by mass, more preferably 20% by mass to less than 50% by mass, still more preferably 25% by mass to less than 45% by mass. When the content of the polyphosphate amine salt flame retardant composition is less than 10% by mass, sufficient flame retardancy may not be exerted, while when the content is 60% by mass or higher, the physical properties intrinsic to the resin may be deteriorated.
Next, the molded article of the present invention will be described. The molded article of the present invention is obtained from the flame-retardant synthetic resin composition of the present invention. A molded article having excellent flame retardancy can be obtained by molding the flame-retardant synthetic resin composition of the present invention. A molding method is not particularly restricted, and examples thereof include extrusion processing, calendar processing, injection molding, rolling, compression molding, and blow molding. Molded articles of various shapes, such as resin plates, sheets, films, fibers and special shape articles, can be produced by these methods.
The flame-retardant synthetic resin composition of the present invention does not foam during processing, and a molded article obtained therefrom has excellent weather resistance and flame retardancy.
The flame-retardant synthetic resin composition of the present invention and a molded article thereof can be used for housings (e.g., frames, casings, covers, and exterior materials) and components of electric vehicles, machines, electric/electronic appliances, office-automation equipment and the like, as well as automobile interior and exterior materials.
The flame-retardant synthetic resin composition of the present invention and a molded article thereof can be used in a wide range of industrial fields, including the fields of electricity/electronics/communication, agriculture/forestry/fisheries, mining, construction, foods, textiles, clothing, health care, coal, petroleum, rubber, leather, automobiles, precision instruments, wood materials, building materials, civil engineering, furniture, printing and musical instruments. More specifically, the flame-retardant synthetic resin composition of the present invention and a molded article thereof can be applied to, for example, office supplies and office-automation equipment, such as printers, personal computers, word processors, keyboards, PDA (Personal Digital Assistant) devices, telephones, copy machines, facsimile machines, ECRs (electronic cash registers), electronic calculators, electronic organizers, cards, holders, and stationery; home electrical appliances, such as laundry machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, gaming machines, irons, and foot warmers; audio-visual equipment, such as TVs, video tape recorders, video cameras, radio-cassette recorders, tape recorders, mini discs, CD players, speakers, and liquid crystal displays; electric and electronic components, such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers, deflection yokes, distribution boards, and clocks; housings (e.g., frames, casings, covers, and exterior materials) and components of communication equipment, office-automation equipment and the like; and automobile interior and exterior materials.
The flame-retardant synthetic resin composition of the present invention and a molded article thereof can also be used in other various applications, for example, materials of automobiles, hybrid cars, electric cars, vehicles, ships, airplanes, buildings and houses, as well as construction and civil engineering materials, such as seats (e.g., stuffing and cover materials), belts, ceiling covers, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, air-bags, insulating materials, straps, strap belts, wire coating materials, electric insulating materials, paints, coating materials, veneer materials, floor materials, baffle walls, carpets, wallpapers, wall decorating materials, exterior materials, interior materials, roof materials, deck materials, wall materials, pillar materials, floor boards, fence materials, framework and molding materials, window and door-shaping materials, shingle boards, sidings, terraces, balconies, soundproof boards, heat insulating boards, and window materials; and household articles and sporting goods, such as clothing materials, curtains, bed linens, plywood boards, synthetic fiber boards, rugs, doormats, leisure sheets, buckets, hoses, containers, eye glasses, bags, casings, goggles, skis, rackets, tents, and musical instruments.
The present invention will now be described concretely by way of Examples thereof. It is noted here, however, that the present invention is not restricted by the following Examples.
In accordance with Production Examples 1 to 7, melamine polyphosphate compositions 1 to 7 were each produced as the polyphosphate amine salt composition of the present invention. In the same manner, comparative melamine polyphosphate compositions 1 and 2 were produced in accordance with Comparative Production Examples 1 and 2. Further, in accordance with Production Examples 8 to 14, piperazine polyphosphate compositions 8 to 14 were each produced as the polyphosphate amine salt composition of the present invention. In the same manner, comparative piperazine polyphosphate compositions 3 and 4 were produced in accordance with Comparative Production Examples 3 and 4. The amount of an orthophosphate amine salt and that of a polyphosphate amine salt in Production Examples 1 to 14 and Comparative Production Examples 1 to 4 were quantified based on the area ratios (%) determined under the following analysis conditions.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monomelamine orthophosphate powder was stirred with heating at a temperature of 220 to 240° C. and a rotation speed of 700 to 1,000 rpm for 2.8 hours to peform a dehydration-condensation reaction, whereby a melamine polyphosphate composition 1 was obtained. As an analysis result, the thus obtained melamine polyphosphate composition 1 contained 0.8% by mass of monomelamine orthophosphate, 99.15% by mass of melamine pyrophosphate, and 0.05% by mass of melamine polyphosphate in which at least three monomelamine orthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monomelamine orthophosphate powder was stirred with heating at a temperature of 220 to 240° C. and a rotation speed of 700 to 1,000 rpm for 3.8 hours to perform a dehydration-condensation reaction, whereby a melamine polyphosphate composition 2 was obtained. As an analysis result, the thus obtained melamine polyphosphate composition 2 contained 0.1% by mass of monomelamine orthophosphate, 99.1% by mass of melamine pyrophosphate, and 0.8% by mass of melamine polyphosphate in which at least three monomelamine orthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monomelamine orthophosphate powder was stirred with heating at a temperature of 220 to 240° C. and a rotation speed of 700 to 1,000 rpm for 3.5 hours to perform a dehydration-condensation reaction, whereby a melamine polyphosphate composition 3 was obtained. As an analysis result, the thus obtained melamine polyphosphate composition 3 contained 0.2% by mass of monomelamine orthophosphate, 99.3% by mass of melamine pyrophosphate, and 0.5% by mass of melamine polyphosphate in which at least three monomelamine orthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monomelamine orthophosphate powder was stirred with heating at a temperature of 220 to 240° C. and a rotation speed of 700 to 1,000 rpm for 3.2 hours to perform a dehydration-condensation reaction, whereby a melamine polyphosphate composition 4 was obtained. As an analysis result, the thus obtained melamine polyphosphate composition 4 contained 0.5% by mass of monomelamine orthophosphate, 99.3% by mass of melamine pyrophosphate, and 0.2% by mass of melamine polyphosphate in which at least three monomelamine orthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monomelamine orthophosphate powder was stirred with heating, at a temperature of 220 to 240° C. and a rotation speed of 700 to 1,000 rpm for 2.5 hours to perform a dehydration-condensation reaction, whereby a melamine polyphosphate composition 5 was obtained. As an analysis result, the thus obtained melamine polyphosphate composition 5 contained 2.0% by mass of monomelamine orthophosphate, 97.95% by mass of melamine pyrophosphate, and 0.05% by mass of melamine polyphosphate in which at least three monomelamine orthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monomelamine orthophosphate powder was stirred with heating at a temperature of 220 to 240° C. and a rotation speed of 700 to 1,000 rpm for 2.2 hours to perform a dehydration-condensation reaction, whereby a melamine polyphosphate composition 6 was obtained. As an analysis result, the thus obtained melamine polyphosphate composition 6 contained 3.0% by mass of monomelamine orthophosphate, 96.95% by mass of melamine pyrophosphate, and 0.05% by mass of melamine polyphosphate in which at least three monomelamine orthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monomelamine orthophosphate powder was stirred with heating at a temperature of 220 to 240° C. and a rotation speed of 700 to 1,000 rpm for 2.1 hours to perform a dehydration-condensation reaction, whereby a melamine polyphosphate composition 7 was obtained. As an analysis result, the thus obtained melamine polyphosphate composition 7 contained 6.0% by mass of monomelamine orthophosphate, 93.95% by mass of melamine pyrophosphate, and 0.05% by mass of melamine polyphosphate in which at least three monomelamine orthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monomelamine orthophosphate powder was stirred with heating at a temperature of 220 to 240° C. and a rotation speed of 700 to 1,000 rpm for 4.5 hours to perform a dehydration-condensation reaction, whereby a comparative melamine polyphosphate composition 1 was obtained. As an analysis result, the thus obtained comparative melamine polyphosphate composition 1 contained 0.05% by mass of monomelamine orthophosphate, 98.85% by mass of melamine pyrophosphate, and 1.1% by mass of melamine polyphosphate in which at least three monomelamine orthophosphate molecules were condensed.
Using a Henschel mixer (FM 150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monomelamine orthophosphate powder was stirred with heating at a temperature of 220 to 240° C. and a rotation speed of 700 to 1,000 rpm for 2.0 hours to perform a dehydration-condensation reaction, whereby a comparative melamine polyphosphate composition 2 was obtained. As an analysis result, the thus obtained comparative melamine polyphosphate composition 2 contained 6.5% by mass of monomelamine orthophosphate, 93.45% by mass of melamine pyrophosphate, and 0.05% by mass of melamine polyphosphate in which at least three monomelamine orthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monopiperazine diorthophosphate powder was stirred with heating at a temperature of 240 to 255° C. and a rotation speed of 700 to 1,000 rpm for 2.5 hours to perform a dehydration-condensation reaction, whereby a piperazine polyphosphate composition 8 was obtained. As an analysis result, the thus obtained piperazine polyphosphate composition 8 contained 0.8% by mass of monopiperazine diorthophosphate 99.15% by mass of piperazine pyrophosphate, and 0.05% by mass of piperazine polyphosphate in which at least three monopiperazine diorthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co. Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monopiperazine diorthophosphate powder was stirred with heating at a temperature of 240 to 255° C. and a rotation speed of 700 to 1,000 rpm for 3.8 hours to perform a dehydration-condensation reaction, whereby a piperazine polyphosphate composition 9 was obtained. As an analysis result, the thus obtained piperazine polyphosphate composition 9 contained 0.1% by mass of monopiperazine diorthophosphate, 99.0% by mass of piperazine pyrophosphate, and 0.9% by mass of piperazine polyphosphate in which at least three monopiperazine diorthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co. Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monopiperazine diorthophosphate powder was stirred with heating at a temperature of 240 to 255° C. and a rotation speed of 700 to 1,000 rpm for 3.2 hours to perform a dehydration-condensation reaction, whereby a piperazine polyphosphate composition 10 was obtained. As an analysis result, the thus obtained piperazine polyphosphate composition 10 contained 0.2% by mass of monopiperazine diorthophosphate, 99.2% by mass of piperazine pyrophosphate, and 0.6% by mass of piperazine polyphosphate in which at least three monopiperazine diorthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monopiperazine diorthophosphate powder was stirred with heating at a temperature of 240 to 255° C. and a rotation speed of 700 to 1,000 rpm for 2.8 hours to perform a dehydration-condensation reaction, whereby a piperazine polyphosphate composition 11 was obtained. As an analysis result, the thus obtained piperazine polyphosphate composition 11 contained 0.5% by mass of monopiperazine diorthophosphate, 99.4% by mass of piperazine pyrophosphate, and 0.1% by mass of piperazine polyphosphate in which at least three monopiperazine diorthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monopiperazine diorthophosphate powder was stirred with heating at a temperature of 240 to 255° C. and a rotation speed of 700 to 1,000 rpm for 2.2 hours to perform a dehydration-condensation reaction, whereby a piperazine polyphosphate composition 12 was obtained. As an analysis result, the thus obtained piperazine polyphosphate composition 12 contained 2.0% by mass of monopiperazine diorthophosphate, 97.95% by mass of piperazine pyrophosphate, and 0.05% by mass of piperazine polyphosphate in which at least three monopiperazine diorthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monopiperazine diorthophosphate powder was stirred with heating at a temperature of 240 to 255° C. and a rotation speed of 700 to 1,000 rpm for 2.0 hours to perform a dehydration-condensation reaction, whereby a piperazine polyphosphate composition 13 was obtained. As an analysis result, the thus obtained piperazine polyphosphate composition 13 contained 3.0% by mass of monopiperazine diorthophosphate 96.95% by mass of piperazine pyrophosphate, and 0.05% by mass of piperazine polyphosphate in which at least three monopiperazine diorthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monopiperazine diorthophosphate powder was stirred with heating at a temperature of 240 to 255° C. and a rotation speed of 700 to 1,000 rpm for 1.8 hours to perform a dehydration-condensation reaction, whereby a piperazine polyphosphate composition 14 was obtained. As an analysis result, the thus obtained piperazine polyphosphate composition 14 contained 6.0% by mass of monopiperazine diorthophosphate, 93.95% by mass of piperazine pyrophosphate, and 0.05% by mass of piperazine polyphosphate in which at least three monopiperazine diorthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monopiperazine diorthophosphate powder was stirred with heating at a temperature of 240 to 255° C. and a
rotation speed of 700 to 1,000 rpm for 4.2 hours to perform a dehydration-condensation reaction, whereby a comparative piperazine polyphosphate composition 3 was obtained. As an analysis result, the thus obtained comparative piperazine polyphosphate composition 3 contained 0.05% by mass of monopiperazine diorthophosphate, 98.75% by mass of piperazine pyrophosphate, and 1.2% by mass of piperazine polyphosphate in which at least three monopiperazine diorthophosphate molecules were condensed.
Using a Henschel mixer (FM150 J/T manufactured by Mitsui Mining Co., Ltd., capacity: 150 L) that had been passed through a heat medium, 25 kg of monopiperazine diorthophosphate powder was stirred with heating at a temperature of 240 to 255° C. and a rotation speed of 700 to 1,000 rpm for 1.7 hours to perform a dehydration-condensation reaction, whereby a comparative piperazine polyphosphate composition 4 was obtained. As an analysis result, the thus obtained comparative piperazine polyphosphate composition 4 contained 6.5% by mass of monopiperazine diorthophosphate, 93.45% by mass of piperazine pyrophosphate, and 0.05% by mass of piperazine polyphosphate in which at least three monopiperazine diorthophosphate molecules were condensed.
To a polypropylene resin composition obtained by blending 60 parts by mass of a polypropylene (melt flow rate=8 g/10 min) with 0.1 parts by mass of calcium stearate (lubricant), 0.1 parts by mass of tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid methyl]methane (phenolic antioxidant), 0.1 parts by mass of tris(2,4-di-tert-butylphenyl)phosphite (phosphorus-based antioxidant) and 0.3 parts by mass of glycerol monostearate (lubricant), the polyphosphate amine salt compositions obtained in Production Examples 1 to 14 and Comparative Production Examples 1 to 4 were each added in the respective amounts (parts by mass) shown in Tables 1 to 3 to obtain flame-retardant synthetic resin compositions of Examples 1 to 19 and Comparative Examples 1 to 6. It is noted here that Tables 1 to 3 also show the content of orthophosphate amine salt in each of the polyphosphate amine salt compositions.
The thus obtained flame-retardant synthetic resin compositions were each extruded using a biaxial extruder (TEX-28, manufactured by The Japan Steel Works, Ltd.) under the conditions of 230° C. and 9 kg/hour to produce pellets, and these pellets were injection-molded at 200° C. into test pieces of 127 mm in length, 12.7 nm in width and 1.6 mm in thickness. Using the thus obtained test pieces, a UL-94V test was conducted as a flame retardancy test in accordance with the below-described test method. The results thereof are shown in Tables 1 to 3.
In addition, using the test pieces, a weather resistance test was conducted in accordance with the below-described test method. Further, the above-obtained flame-retardant synthetic resin compositions were each extruded using a biaxial extruder (TEX-28, manufactured by The Japan Steel Works, Ltd.) under the conditions of 230° C. and 13 kg/hour to produce pellets or evaluation of workability. For the thus obtained pellets for evaluation of workability, the surface state was visually observed to check the presence or absence of foaming, and the workability was evaluated based on the below-described evaluation criteria. The results thereof are shown in Tables 1 to 3.
Each test piece of 127 mm in length, 12.7 mm in width and 1.6 mm in thickness was held vertically, and a burner flame was brought into contact with the lower end of the test piece for 10 seconds. Subsequently, the flame was removed, and the time required for the flame ignited on the test piece to be extinguished was measured. Next, simultaneously with the flame extinction, a flame was again brought into contact with the test piece for 10 seconds, and the time required for the flame ignited on the test piece to be extinguished was measured in the same manner as in the first measurement. In addition, at the same time, it was evaluated whether or not a piece of cotton placed under the test piece was ignited by cinders falling from the test piece. Based on the first and the second combustion times, the presence or absence of ignition of the cotton piece, and the like, the condition of combustion was rated in accordance with the UL-94V standard. The combustion rating of V-0 indicates the most excellent flame retardancy, and the flame retardancy decreases in the order of v-1 and V-2, with the rating of NR representing the lowest flame retardancy.
The above-obtained test pieces were each subjected to an accelerated weather resistance test using a Sunshine Weather Meter (manufactured Suga Test Instruments Co., Ltd.) under the following conditions: with rainfall, at a black panel temperature of 63° C., for a period of up to 800 hours. The yellowness (YI) at 0 hours (initial value) and at 800 hours as well as the change in yellowness (ΔYI) were measured for each test piece. A smaller change in yellowness (ΔYI) indicates superior weather discoloration resistance.
Fifty pellets were randomly selected, and the presence or absence of foaming on the surfaces of the pellets was visually checked and evaluated on a 5-point scale. As for the evaluation, a score of 1 was given when the workability was most favorable with no foaming mark on surfaces of all pellets. A higher evaluation score means that more foaming marks were observed on the surfaces of the pellets, with a score of 5 indicating very poor workability with observation of foaming marks on the surface of all pellets.
From the results shown in Tables 1 to 3, it is seen that polyphosphate amine salt compositions which do not foam during processing and not only have excellent workability and excellent weather resistance but also can impart excellent flame retardancy to synthetic resins, as well as polyphosphate amine salt flame retardant compositions and flame-retardant synthetic resin compositions containing the same were obtained. Further, from the results shown in Tables 1 to 3, it is seen that, according to the present invention, molded articles having excellent weather resistance and flame retardancy can be easily obtained by processing the respective compositions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-112709 | Jun 2018 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2019/023307 | 6/12/2019 | WO | 00 |
