TW202309254A - Flame retardant agent composition, flame retardant resin composition, and molded article thereof - Google Patents

Abstract

Provided are: a novel flame retardant agent composition having excellent flame retardancy; a flame retardant resin composition; and a molded article thereof. This flame retardant agent composition contains: a component (A) which is at least one compound selected from the group consisting of a polyphosphate compound and an orthophosphate compound; and a component (B) which is at least one compound selected from the group consisting of a fatty acid and a fatty acid metal salt. If the electrical conductivity of a mixed liquid comprising 100 parts by mass of ultrapure water and 1 part by mass of the flame retardant agent composition is denoted by EC ([mu]S/cm), then EC satisfies formula (I): 0.1*10<SP>3</SP> ≤ EC ≤ 2.4*10<SP>3</SP>.

Description

Flame retardant composition, flame retardant resin composition and molded article thereof

The present invention relates to a flame retardant composition, a flame retardant resin composition, and its molded articles, and more specifically, to a novel flame retardant composition, a flame retardant resin composition, and its molded articles having excellent flame retardancy.

Synthetic resin is used in a wide range of fields due to its excellent mechanical properties and high convenience, and has become an indispensable material for modern life. On the other hand, many synthetic resins are flammable, and it is important to impart flame retardancy in order to improve safety depending on the application. As a method of imparting flame retardancy to synthetic resins, flame retardants are widely added, and halogen-based flame retardants are mainly used because they are excellent in flame retardancy.

However, halogen-based flame retardants have problems such as thermal decomposition during resin molding to generate hydrogen halides, which cause corrosion of molds and discoloration of resins. In addition, since the halogen-based flame retardants generate hydrogen halides and carbon monoxide harmful to the human body during combustion, and generate a large amount of smoke, there is a problem of safety in the event of a fire. In addition, halogen-based flame retardants are often used in combination with antimony trioxide as a flame retardant aid, which may cause health damage to workers who handle them.

For these problems, non-halogen flame retardants have been widely used. As such a technique, it is known, for example, to add a small amount of a phosphate-based flame retardant to exert high flame retardancy. Such flame retardants are proposed in Patent Document 1, for example. Patent Document 1 discloses that a flame retardant composition containing a specific phosphate compound, fatty acid, etc. has excellent flame retardancy and does not easily cause secondary aggregation. [Prior Art Literature] [Patent Document]

Patent Document 1: International Publication No. 2004/000973

[Problem to be solved by the invention]

However, the performance of the flame retardant composition proposed in Patent Document 1 cannot be said to be sufficient, and there is still room for improvement in terms of flame retardancy.

Therefore, an object of the present invention is to provide a novel flame retardant composition, a flame retardant resin composition, and a molded article thereof having excellent flame retardancy. [Means to solve the problem]

As a result of active research on this subject, the present inventors have discovered the relationship between conductivity and flame retardancy of a mixture of a flame retardant composition containing a phosphate-based flame retardant, a fatty acid or its salt, and ultrapure water. As a result of further intensive studies, the present inventors found that the flame retardancy was further improved by surface-treating the phosphate-based flame retardant with a fatty acid or a fatty acid metal salt. In addition, the inventors of the present invention also found that by adding a silicate compound to the flame retardant composition, the calorific value and smoke generation during combustion can be suppressed, and thus completed the present invention.

此處所謂超純水係指導電度為5.5×10 ^-2(μS/cm)以下的純水。 That is, the flame retardant composition of the present invention is characterized by containing: (A) component: at least one compound selected from the group consisting of polyphosphate compounds and orthophosphate compounds, and (B) component: selected from fatty acids At least one compound of the group consisting of metal salts of fatty acids, when the electrical conductivity of a mixture of 100 parts by mass of ultrapure water and 1 part by mass of the aforementioned flame retardant composition is EC (μS/cm), EC satisfies the following Formula (I),

Here, the ultrapure water refers to pure water having a conductivity of 5.5×10 ^-2 (μS/cm) or less.

In the flame retardant composition of the present invention, it is preferable that the aforementioned component (A) is surface-treated by the aforementioned component (B).

In the flame retardant composition of the present invention, it is preferable that the aforementioned (A) component is one or more types selected from the group consisting of the following (a1) component and the following (a2) component.

通式(1)中，n1表示1~100之數，X ¹表示氨或以下述通式(1-A)表示之三嗪衍生物，p表示滿足0＜p≦n1+2之數。 (a1) Component: a compound represented by the following general formula (1).

In the general formula (1), n1 represents a number from 1 to 100, ^X1 represents ammonia or a triazine derivative represented by the following general formula (1-A), and p represents a number satisfying 0<p≦n1+2.

通式(1-A)中，Z ¹及Z ²各自獨立表示選自由-NR ¹¹R ¹²基、羥基、巰基、碳原子數1~10之直鏈或分支之烷基、碳原子數1~10之直鏈或分支之烷氧基、苯基及乙烯基所成之群之任一種基，R ¹¹及R ¹²各自獨立表示氫原子、碳原子數1~6之直鏈或分支之烷基或羥甲基。

In the general formula (1-A), Z ¹ and Z ² each independently represent a group selected from -NR ¹¹ R ¹² groups, hydroxyl groups, mercapto groups, linear or branched alkyl groups with 1 to 10 carbon atoms, and alkyl groups with 1 to 10 carbon atoms. 10 Any one of the group of straight-chain or branched alkoxy, phenyl and vinyl groups, ^R11 and ^R12 each independently represent a hydrogen atom, straight-chain or branched alkyl group with 1 to 6 carbon atoms or hydroxymethyl.

通式(2)中，n2表示1~100之數，Y ¹表示[R ²¹R ²²N(CH ₂) _mNR ²³R ²⁴]、哌嗪或包含哌嗪環之二胺，R ²¹、R ²²、R ²³及R ²⁴各自獨立表示氫原子、或碳原子數1~5之直鏈或分支之烷基，m係1~10之整數，q表示滿足0＜q≦n2+2之數。 (a2) Component: a compound represented by the following general formula (2).

In general formula (2), n2 represents a number from 1 to 100, Y ¹ represents [R ²¹ R ²² N(CH ₂ ) _m NR ²³ R ²⁴ ], piperazine or diamine containing a piperazine ring, R ²¹ , R ^22. R ²³ and R ²⁴ each independently represent a hydrogen atom, or a linear or branched alkyl group with 1 to 5 carbon atoms, m is an integer from 1 to 10, and q represents a number satisfying 0<q≦n2+2.

通式(3)中，R ³¹表示自碳原子數10~30之脂肪酸去除羧基之殘基，M ¹表示氫、鋰、鈉、鉀、鎂、鈣、鋇、鋅或Al(OH) _3-r，r表示1~3之整數。 In the flame retardant composition of the present invention, it is preferable that the aforementioned (B) component is a compound represented by the following general formula (3).

In the general formula (3), R ³¹ represents the residue of removing the carboxyl group from a fatty acid with 10 to 30 carbon atoms, and M ¹ represents hydrogen, lithium, sodium, potassium, magnesium, calcium, barium, zinc or Al(OH) _{3- r} , r represents an integer from 1 to 3.

In the flame retardant composition of the present invention, it is preferable that the aforementioned component (B) contains one or more compounds in which M ¹ in the general formula (3) is selected from hydrogen and calcium.

In the flame retardant composition of the present invention, it is preferable that the aforementioned component (A) includes the component (a1) in which X ¹ is melamine in the general formula (1).

In the flame retardant composition of the present invention, it is preferable that the aforementioned component (A) includes the component (a2) in which Y ¹ in the general formula (2) is piperazine.

In the flame retardant composition of the present invention, the aforementioned component (A) preferably includes: component (a1) in which n1 is 2 in general formula (1), and component (a2) in which n2 is 2 in general formula (2).

In the flame retardant composition of the present invention, it is preferable to further contain 1 to 30 parts by mass of the component (C): a silicate compound with respect to a total of 100 parts by mass of the component (A) and the component (B).

Furthermore, the flame retardant resin composition of the present invention is characterized by containing the above-mentioned flame retardant composition and a thermoplastic resin.

In the flame retardant resin composition of the present invention, it is preferable to further contain glass fibers.

Furthermore, the molded article of the present invention is characterized by using the above-mentioned flame retardant resin composition. [Invention effect]

According to the present invention, a novel flame retardant composition having excellent flame retardancy, a flame retardant resin composition, and a molded article thereof can be provided.

The present invention relates to a flame retardant composition, a flame retardant resin composition, and molded articles thereof. The present invention will be described below based on preferred embodiments.

＜Flame retardant composition＞ In this specification, polyphosphoric acid means one or more kinds of pyrophosphoric acid having a condensation degree of 2, and condensed phosphoric acid having a condensation degree of 3 or more, or a mixture thereof. In addition, the polyphosphate refers to the salt compound formed by the said polyphosphoric acid and alkali.

。 The flame retardant composition of the present invention contains at least one compound selected from the group consisting of polyphosphate compounds and orthophosphate compounds as the component (A), and a compound selected from fatty acids and fatty acid metals as the component (B) Phosphate-based flame retardants consisting of at least one compound in the group of salts, when the electrical conductivity of the mixed solution with ultrapure water measured according to the following procedure is EC (μS/cm), EC satisfies the following formula ( I),

.

The procedure for measuring the electrical conductivity EC of the above mixed solution is as follows. For 100 parts by mass of ultrapure water, mix 1 part by mass of the above-mentioned flame retardant composition as a sample, stir at 22°C with a magnetic stirring bar at 240~300rpm for 10 minutes, and then let it stand in a constant temperature water tank at 30°C for 5 minutes , as the assay solution. The conductivity was measured for the obtained measurement solution using a conductivity meter.

As an apparatus for stirring the above liquid mixture, for example, a stirrer using a stirring blade, a magnetic stirring bar, a headspace stirrer, a static mixer using a liquid flow, etc. can be used. In addition, when measuring electrical conductivity, a commercially available conductivity meter (conductivity meter) can also be used.

The upper limit of the electrical conductivity EC of the formula (I) is 2.4×10 ³ or less. On the other hand, the lower limit of EC is at least 0.1×10 ³ , preferably at least 0.5×10 ³ , more preferably at least 0.8×10 ³ .

The flame retardant composition of the present invention obtains the effect of improving flame retardancy when the electrical conductivity EC satisfies the formula (I). The details of the reason are unclear, but it is presumed as follows. That is to say, it is believed that by making the electrical conductivity EC within the range of formula (I), the (A) component and (B) component form a better intermolecular interaction, as a result, the aggregation of the flame retardant is suppressed, and the dispersion in the resin is improved. Therefore, it improves the flame retardancy.

In the flame retardant composition of the present invention, the electrical conductivity EC can be controlled by, for example, appropriately selecting the type and amount of each component contained in the flame retardant composition, the method for producing the flame retardant composition, and the like. Among these, the factors used to set the electrical conductivity EC as a preferable value range are, for example, the synthesis process using polyphosphate or orthophosphate or the manufacture of flame retardant compositions using polyphosphate or orthophosphate Eliminate the mixing of impurities as much as possible during the process, and properly select the conditions for surface treatment of (A) component with (B) component, etc. And if necessary, arbitrary components, such as a surface treatment agent other than (B) component, can also be used together.

In the flame retardant composition of the present invention, it is preferable that component (A) is surface-treated with component (B). As mentioned above, as one of the means which makes electrical conductivity EC into a preferable numerical range, surface-treating (A) component with (B) component is mentioned, for example. Surface treatment is the easiest way to adjust the conductivity EC.

The surface treatment method is not particularly limited, for example, a method of mixing a powder composition containing (A) component and (B) component, spray-drying (B) component to the composition containing (A) component, and then adding and mixing method etc.

The device used for the surface treatment is not particularly limited, but examples include, for example, a drum mixer, a Henschel mixer, a ribbon blender, a V-type mixer, a W-type mixer, a super mixer, and a Nauta mixer , Single-screw extruder, twin-screw extruder, food mixer, etc.

It can also be heated during surface treatment. The temperature during surface treatment is preferably 40° C. or higher from the viewpoint of efficiently progressing the surface treatment step. And, the temperature at the time of surface treatment is preferably higher than the melting point of (B) component when the (B) component has a melting point, more preferably 5° C. or more higher than the melting point of (B) component. Thereby, surface treatment can be performed uniformly efficiently. In addition, the temperature during the surface treatment is preferably not higher than 200°C, more preferably not higher than 180°C, and still more preferably not higher than 170°C. Thereby, coloring of the flame retardant composition can be suppressed.

The (A) component in the flame retardant composition of the present invention is preferably one or more types selected from the following (a1) component and (a2) component. The component (a1) is a compound represented by the following general formula (1).

In the general formula (1), n1 represents a number from 1 to 100, ^X1 represents ammonia or a triazine derivative represented by the following general formula (1-A), and p represents a number satisfying 0<p≦n1+2.

In the general formula (1-A), Z ¹ and Z ² each independently represent a group selected from -NR ¹¹ R ¹² groups, hydroxyl groups, mercapto groups, linear or branched alkyl groups with 1 to 10 carbon atoms, and alkyl groups with 1 to 10 carbon atoms. 10 Any one of the group of straight-chain or branched alkoxy, phenyl and vinyl groups, ^R11 and ^R12 each independently represent a hydrogen atom, straight-chain or branched alkyl group with 1 to 6 carbon atoms or hydroxymethyl.

As a linear or branched alkyl group with 1 to 10 carbon atoms represented by ^Z1 and ^Z2 in the general formula (1-A), for example, methyl, ethyl, propyl, isopropyl, butyl, Second butyl, third butyl, isobutyl, pentyl, isopentyl, third pentyl, neopentyl, hexyl, cyclohexyl, heptyl, isoheptyl, third heptyl, n-octyl , isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, decyl, etc., as a straight chain or branched alkoxy group having 1 to 10 carbon atoms, examples are groups derived from these alkyl groups . In addition, the straight-chain or branched alkyl groups with 1 to 6 carbon atoms represented by R ¹¹ and R ¹² in the -NR ¹¹ R ¹² group that can be used as Z ¹ and Z ² are exemplified by carbon in the above-mentioned alkyl groups Atomic number 1~6.

Specific examples of triazine derivatives represented by the general formula (1-A) include melamine, acetylguanidine, benzoguanidine, guanidine acrylate, 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, 2-amino-4,6-dimercapto-1,3,5-triazine, etc.

(a1) The component may be a single compound, or may be a mixture of two or more different types of condensation or salt. The component (a1) preferably contains at least one of a melamine salt compound in which X ¹ in the general formula (1) is melamine and an ammonium salt compound in which X ¹ in the general formula (1) is ammonia. Also, the component (a1) preferably includes pyrophosphate in which n1 is 2 in the general formula (1). When used as a mixture, the higher the content ratio of the pyrophosphate in which n1 is 2, the better. Thereby, heat resistance can be improved stably.

The component (a2) is a compound represented by the following general formula (2).

In general formula (2), n2 represents a number from 1 to 100, Y ¹ represents [R ²¹ R ²² N(CH ₂ ) _m NR ²³ R ²⁴ ], piperazine or diamine containing a piperazine ring, R ²¹ , R ^22. R ²³ and R ²⁴ each independently represent a hydrogen atom, or a linear or branched alkyl group with 1 to 5 carbon atoms, m is an integer from 1 to 10, and q represents a number satisfying 0<q≦n2+2.

In the general formula (2), the compound represented by Y ¹ is exemplified by [R ²¹ R ²² N(CH ₂ ) _m NR ²³ R ²⁴ ], piperazine, or diamine containing a piperazine ring. R ²¹ to R ²⁴ may be the same or different, and represent a hydrogen atom or a linear or branched alkyl group with 1 to 5 carbon atoms.

Examples of straight-chain or branched alkyl groups having 1 to 5 carbon atoms represented by R ²¹ to R ²⁴ include, for example, the number of carbon atoms in the specific examples of the alkyl groups represented by Z ¹ and Z ² above. 1~5 persons.

Examples of diamines containing a piperazine ring include, for example, compounds in which one or more of the 2, 3, 5, and 6 positions of piperazine are substituted by an alkyl group, preferably an alkyl group with 1 to 5 carbon atoms; A compound wherein the amino group at the 1-position and/or 4-position is substituted by an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms.

As the compound represented by ^Y1 in the general formula (2), specific examples are N,N,N',N'-tetramethyldiaminomethane, ethylenediamine, N,N'-dimethylethylenediamine , N,N'-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine Amine, N,N,N',N'-tetraethylethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexa Methylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, piperazine, trans Formula - 2,5-dimethylpiperazine, 1,4-bis(2-aminoethyl)piperazine, 1,4-bis(3-aminopropyl)piperazine, etc.

The (a2) component may be a single compound or a mixture of two or more different types of condensation or salt. The component (a2) preferably includes a piperazine salt compound in which Y ¹ in the general formula (2) is piperazine. And, it is preferable that the component (a2) contains pyrophosphate in which n2 is 2 in general formula (2). When used as a mixture, the higher the content ratio of pyrophosphate with n2 being 2, the better. Thereby, heat resistance can be improved stably.

As a method for producing the compounds represented by the general formula (1) and the general formula (2), for example, as a salt of phosphoric acid and melamine pyrophosphate, sodium pyrophosphate and melamine can be mixed in any ratio, and hydrochloric acid is added to make it Reaction, and obtained by neutralization with sodium hydroxide. Also, for example, the salt of phosphoric acid and piperazine can be reacted in water or methanol aqueous solution at any ratio, and can be easily obtained as a poorly water-soluble precipitate. At this time, the composition of phosphoric acid as a raw material is not particularly limited. Moreover, the phosphate compound in which n1 or n2 is 2 or more in general formula (1) or general formula (2) can also be obtained by thermally condensing orthophosphate with n1 or n2 being 1.

Through the above, the compounds represented by the general formula (1) and the general formula (2) are obtained. These may be used alone or in combination of two or more. A flame retardant composition containing these compounds can impart excellent flame retardancy to resin materials.

In the flame retardant composition of the present invention, it is preferable that (A) component contains both (a1) component and (a2) component from a viewpoint of flame retardancy. In particular, among the components (A), it is more preferable to use the component (a1) in which X ¹ is melamine in the general formula (1) and the component (a2) in which Y ¹ is piperazine in the general formula (2). Furthermore, in the component (A), it is also preferable to use the component (a1) in which n1 is 2 in the general formula (1) and the component (a2) in which n2 is 2 in the general formula (2) in combination.

In the flame retardant composition of the present invention, when the component (A) contains both the component (a1) and the component (a2), the content ratio is preferably 20 in mass ratio between the former and the latter from the viewpoint of flame retardancy. :80~60:40, more preferably 25:75~55:45, and more preferably 30:70~50:50.

The component (B) of the flame retardant composition of the present invention is preferably a component represented by the following general formula (3).

In the general formula (3), R ³¹ represents the residue of removing the carboxyl group from a fatty acid with 10 to 30 carbon atoms, and M ¹ represents hydrogen, lithium, sodium, potassium, magnesium, calcium, barium, zinc or Al(OH) _{3- r} , r represents an integer from 1 to 3.

As the residue represented by R ³¹ in the general formula (3) from a fatty acid having 10 to 30 carbon atoms after removing the carboxyl group, examples include an alkyl group and an alkenyl group having 9 to 29 carbon atoms, and two or more unsaturated bonds introduced Hydrocarbon groups such as alkyl groups. These may be linear or branched, and a part of hydrogen in the hydrocarbon chain may be substituted by hydroxyl groups.

The number of carbon atoms of the hydrocarbon group represented by R ³¹ in the general formula (3) is preferably in the range of 9-21, more preferably in the range of 11-17.

Specific examples of fatty acids with 10 to 30 carbon atoms include capric acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearlescent fatty acid, stearic acid, Saturated fatty acids such as fatty acid, nonadecanoic acid, arachidic acid, behenic acid, behenic acid, tricosanoic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, etc., 4-decenoic acid , 4-dodecenoic acid, palmitoleic acid, α-linolenic acid, linoleic acid, γ-linolenic acid, stearidonic acid, petroleum ether acid, oleic acid, trans oleic acid, vacantoleic acid, Linear unsaturated fatty acids such as eicosapentaenoic acid, docosapentaenoic acid, and docosahexaenoic acid, etc. Also, a part of the hydrocarbon chains of these fatty acids may be substituted with hydroxyl groups. Among these, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, oleic acid, and linoleic acid are preferred, and lauric acid, myristic acid, and Myristic acid, palmitic acid, stearic acid, more preferably stearic acid.

(B) Component, based on the viewpoint of making the effect of the present invention remarkable, preferably comprises M in general formula (3) ¹ or more compounds selected from hydrogen, lithium, sodium, magnesium, calcium, barium and zinc, More preferably, it includes a compound in which M ¹ is at least one type selected from hydrogen and calcium, and more preferably includes a compound in which M ¹ is hydrogen.

The component (B) may be a single compound or a mixture of two or more different R ³¹ and/or M ¹ in the general formula (3).

In the flame retardant composition of the present invention, the component (B) preferably contains at least one kind selected from stearic acid and calcium stearate, and particularly preferably contains stearic acid, from the viewpoint of making the effect of the present invention remarkable.

The amount of component (B) in the flame retardant composition of the present invention is preferably 0.001-10 parts by mass, more preferably 0.005-3 parts by mass, and even more preferably 0.01 parts by mass relative to 100 parts by mass of component (A). ~1 part by mass. When it is less than 0.001 parts by mass, the effects of the present invention may not be obtained, and when it exceeds 10 parts by mass, molded articles obtained by molding a flame-retardant resin composition described later may be colored.

The flame retardant composition of the present invention may contain optional components described below other than the (A) component and the (B) component as needed.

Various mixers can be used for mixing. It can also be heated while mixing. Examples of usable mixers are exemplified by tumble mixers, Henschel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, Natta mixers, and the like.

The flame retardant composition of the present invention preferably contains component (C): a silicate compound. Thereby, flame retardancy is improved, and smoke during combustion can be suppressed.

Examples of the silicate compound include talc, kaolin, clay, mica, montmorillonite, zeolite, feldspar and the like. Among these, talc, kaolin, clay, and mica are preferred from the viewpoint of flame retardancy, and talc and kaolin are more preferred. These may be used alone or in combination of two or more. These silicate compounds may or may not be surface-treated.

The blending amount of component (C) in the flame retardant composition of the present invention is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, based on 100 parts by mass of the total of components (A) and (B) parts, more preferably 5 to 18 parts by mass. Thereby, the effects of the present invention can be sufficiently obtained.

The flame retardant composition of the present invention may also contain additives. As an auxiliary agent, a flame retardancy auxiliary agent, an anti-dripping auxiliary agent, a processing aid etc. are mentioned, for example. The flame retardant aid may contain metal oxides or polyol compounds. Thereby, the flame retardancy of the resin can be improved.

Examples of metal oxides include titanium oxide, zinc oxide, calcium oxide, magnesium oxide, zirconium oxide, barium oxide, tin dioxide, lead dioxide, antimony oxide, molybdenum oxide, and cadmium oxide. These may be used alone or in combination of two or more. Thereby, the flame retardancy of the resin can be improved. In addition, it is possible to suppress aggregation in the powdery and granular flame retardant composition. Also, from the viewpoint of flame retardancy, zinc oxide is preferred. The zinc oxide may or may not be surface-treated.

As zinc oxide, for example, one type of zinc oxide (manufactured by Mitsui Kinzoku Industries Co., Ltd.), partially coated zinc oxide (manufactured by Mitsui Kinzoku Industries Co., Ltd.), Nanofine 50 (ultrafine particle zinc oxide with an average particle diameter of 0.02 μm) can also be used. : Sakai Chemical Industry Co., Ltd.), Nanofine K (ultrafine particle zinc oxide coated with zinc silicate with an average particle diameter of 0.02 μm: Sakai Chemical Industry Co., Ltd. product) and other commercially available products.

As the polyhydric alcohol, it is a compound to which a plurality of hydroxyl groups are bonded, such as pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, di-trimethylolpropane, 1 ,3,5-ginseng (2-hydroxyethyl) isocyanurate (THEIC), polyethylene glycol, glycerin, diglycerin, mannitol, maltitol, lactitol, sorbitol, erythritol, wood Sugar alcohol, xylose, sucrose, trehalose, inositol, fructose, maltose, lactose, etc. Among these polyol compounds, one or more selected from the group of pentaerythritol and pentaerythritol condensates such as pentaerythritol, dipentaerythritol, tripentaerythritol, and polypentaerythritol is preferred, and dipentaerythritol and pentaerythritol condensates are particularly preferred. Preferred is dipentaerythritol. Furthermore, THEIC and sorbitol are also preferably used. These may be used alone or in combination of two or more.

Examples of anti-dripping additives include layered silicate, fluorine-based anti-dripping additives, and silicone rubbers. This can suppress dripping when the resin burns.

The phyllosilicate is a phyllosilicate mineral, which may be natural or synthetic, and is not particularly limited. Examples of phyllosilicates include montmorillonite-based clay minerals such as montmorillonite, saponite, hectorite, bayleyite, stevensite, nontronite, etc., and vermiculite, wokolite, swelling Mica, talc, etc. These may be used alone or in combination of two or more. Among these, soapstone or talc is preferable from the viewpoint of anti-dripping, and talc is particularly preferable from the viewpoint of economics such as price.

The phyllosilicate may have cations between the layers. The cations may be metal ions, or part or all of them may be cations other than metal ions such as organic cations, (quaternary) ammonium cations, and phosphonium cations.

Examples of metal ions include sodium ions, potassium ions, calcium ions, magnesium ions, lithium ions, nickel ions, copper ions, zinc ions and the like.

As organic cations or quaternary ammonium cations, for example, lauryltrimethylammonium cation, stearyltrimethylammonium cation, trioctylmethylammonium cation, distearyldimethylammonium cation, dihardened tallow Dimethylammonium cation, distearyldibenzylammonium cation, and the like. These may be used alone or in combination of two or more.

Specific examples of fluorine-based anti-dripping additives include fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride, and hexafluoropropylene, or sodium salt of perfluoromethanesulfonate, potassium salt of perfluoro-n-butanesulfonate Perfluoroalkane sulfonic acid alkali metal salt compounds or perfluoroalkane sulfonic acid Alkaline earth metal salts, etc. Among these, polytetrafluoroethylene is preferred from the viewpoint of anti-dripping properties. These may be used alone or in combination of two or more.

As the processing aid, it can be appropriately selected from conventional processing aids, but acrylic processing aids may also be included.

As acrylic processing aids, for example, homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; the aforementioned alkyl methacrylates and acrylic acid Copolymers of alkyl acrylates such as methyl ester, ethyl acrylate, and butyl acrylate; copolymers of the aforementioned alkyl methacrylates and aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; the aforementioned methyl acrylates Copolymers of alkyl acrylates and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, etc. These may be used alone or in combination of two or more.

The flame retardant composition of the present invention may also contain a surface treatment agent. Examples of surface treatment agents include silicone oil and silane coupling agents.

By using silicone oil as a surface treatment agent, it is possible to prevent aggregation of the powdered flame retardant composition, improve storage stability, and improve dispersibility to synthetic resins. And water resistance can be improved.

The silicone oil can be used without particular limitation as long as it is a conventional silicone oil having a polysiloxane skeleton. The silicone oil can be a polymer with a straight-chain polysiloxane skeleton, and the side chains of the polysiloxane can all be methyl groups, or a part of the side chains can have phenyl groups, or a part of the side chains can have hydrogen.

Examples of silicone oils include dimethyl silicone oil in which the side chains and terminals of polysiloxane are all methyl groups; the side chains and terminals of polysiloxane are methyl groups, and part of the side chains is methyl groups. Phenyl silicone oil; methyl hydrogen silicone oil, etc., in which the side chain and terminal of polysiloxane are methyl groups, and part of the side chain is hydrogen, or their copolymers. These silicone oils can be partially modified by epoxy modification, amino modification, carboxyl modification, etc. These may be used alone or in combination of two or more.

Among silicone oils, dimethyl silicone oil and methyl hydrogen silicone oil are preferred, and methyl hydrogen silicone oil is more preferred from the viewpoint of preventing aggregation of powdered flame retardant compositions, improving storage stability, and improving dispersibility to synthetic resins. .

The method of adding the surface treatment agent includes, for example, a method of mixing a powdery flame retardant composition and a surface treatment agent, a method of spray-drying a surface treatment agent and adding and mixing, and the like. In addition, the surface treatment agent may be added to the flame retardant composition by surface treating a part of the components of the flame retardant composition.

As a silane coupling agent, for example, as a silane coupling agent having an alkenyl group, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinylparaffin (2-methoxy ethoxy)silane, vinylmethyldimethoxysilane, octenyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, etc., as silanes with acrylic groups Coupling agents, for example, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, etc., as silane coupling agents with methacrylic groups, for example, 3-methoxysilane Acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- Methacryloxypropyltriethoxysilane, methacryloxyoctyltrimethoxysilane, etc., as silane coupling agents with epoxy groups, 2-(3,4-epoxy Cyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Diethoxysilane, 3-glycidoxypropyltriethoxysilane, glycidoxyoctyltrimethoxysilane, etc., as silane coupling agents with amino groups, can be exemplified by N-2-(amine N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxy N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxy Silane hydrochloride, etc., as a silane coupling agent with an isocyanurate group, can be exemplified by ginseng-(trimethoxysilylpropyl) isocyanurate, as a silane coupling agent with a mercapto group, can be For example, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc., as the silane coupling agent with ureido group, can be 3 - Ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, etc. As a silane coupling agent with a thioether group, bis(triethoxysilylpropyl)tetrasulfide can be exemplified , as a silane coupling agent with a thioester group, for example, 3-octylthio-1-propyltriethoxysilane, as a silane coupling agent with an isocyanate group, for example, 3-isocyanatopropyl triethoxysilane Ethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc. These may be used alone or in combination of two or more.

Among these silane coupling agents, silane coupling agents with epoxy groups are preferred, more preferably 2-( 3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidyloxy Propylmethyldiethoxysilane, 3-Glycidoxypropyltriethoxysilane, Glycidoxyoctyltrimethoxysilane.

The flame retardant composition of the present invention may also contain a dust suppressant. As a dust suppressant, an aliphatic dicarboxylic acid ether ester compound, the above-mentioned silane coupling agent, etc. are mentioned, for example.

The aliphatic dicarboxylic acid ether ester compound may contain a compound represented by the following general formula (4). Thereby, the dustiness of the powdery flame retardant composition can be suppressed. These may be used alone or in combination of two or more.

In the general formula (4), n4 represents an integer of 1 to 3, m4 represents an integer of 2 to 6, and ^R41 represents an alkyl group having 1 to 6 carbon atoms.

In the general formula (4), the alkyl group having 1 to 6 carbon atoms may be a straight-chain alkyl group or a branched alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, isopropyl, etc. Butyl, second butyl, third butyl, pentyl, isopentyl, third pentyl, hexyl, etc. From the standpoint of flame retardancy, especially handleability and storage stability, R ⁴¹ is preferably a butyl group.

In the general formula (4), n4 is preferably 2 from the viewpoint of flame retardancy, especially handleability and storage stability. Furthermore, in the general formula (4), m4 is preferably 4 from the viewpoint of flame retardancy, especially handleability, and storage stability.

The flame retardant composition of the present invention may also contain other components within the range that does not impair the effect of the present invention. As other components, additives generally used for modifying thermoplastic resins can be used, but for example, antioxidants, light stabilizers, ultraviolet absorbers, crystal nucleating agents, clearing agents, plasticizers, slip agents, the present invention Flame retardants, reinforcements, crosslinking agents, antistatic agents, metal soaps, fillers, antifogging agents, anti-bleeding agents, fluorescent agents, antifungal agents, Bactericides, foaming agents, metal inert agents, mold release agents, pigments, dyes, etc. These may be used alone or in combination of two or more.

Examples of antioxidants include phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and other antioxidants.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5 - Di-tert-butyl-4-hydroxyphenyl) phosphite, 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide ], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2, 2'-Methylene bis(4-ethyl-6-tert-butylphenol), 4,4'-butylene bis(6-tert-butyl-m-cresol), 2,2'- Ethylbis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(4-second-butyl-6-tert-butylphenol), 1,1,3-reference (2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-paraffin(2,6-dimethyl-3-hydroxy-4-tert-butylphenyl ) isocyanurate, 1,3,5-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-ginseng (3,5- Di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-th Tributyl-5-methylbenzyl)phenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6 -Hexamethylenebis[(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] terephthalylene ester, 1,3,5-paraffin[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 3,9-bis[1, 1-Dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[ 5,5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], etc. These phenolic antioxidants may be used individually by 1 type, and may use 2 or more types together.

Examples of phosphite antioxidants include ginseng nonylphenyl phosphite, ginseng [2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio) )-5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, didecyl monophenyl phosphite, bis(tridecyl) pentaerythritol disulfide Phosphate, bis(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, tetrakis(tridecyl)isopropylidene diphenol diphosphite, tetrakis(tridecyl)-4,4'-n-butylene bis(2-tert-butyl-5 -methylphenol)diphosphite, Lu(tridecyl)-1,1,3-ginseng(2-methyl-4-hydroxy-5-tert-butylphenyl)butanetriphosphite, Tetra(2,4-di-tert-butylphenyl) biphenyl diphosphonite, 9,10-dihydro-9-oxa-10-phosphoxanthene-10-oxide, 2,2 '-Methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)- Octadecyl phosphite, 2,2'-ethylenebis(4,6-di-tert-butylphenyl) fluorophosphite, ginseng (2-[(2,4,8,10- (4-tert-butyldibenzo[d,f][1,3,2]dioxaphosphorin-6-yl)oxy]ethyl)amine, 2-ethyl-2-butanol Phosphite ester of propanediol and 2,4,6-tri-tert-butylphenol, etc. These phosphite-based antioxidants may be used alone or in combination of two or more.

Examples of thioether-based antioxidants include 3,3'-thiodipropionic acid, alkyl (C12-14)thiopropionic acid, di(lauryl)-3,3'-thiodipropionate, Di-tridecyl 3,3'-thiodipropionate, Di(myristyl)-3,3'-thiodipropionate, Di(stearyl)-3,3'-thio dipropionate, bis(octadecyl)-3,3'-thiodipropionate, laurylstearylthiodipropionate, tetrakis[methylene-3-(dodecyl Thio)propionate]methane, Thiobis(2-tert-butyl-5-methyl-4,1-phenylene)bis(3-(dodecylthio)propionate), 2,2'-thiobis(3-aminobutenoate), 4,6-bis(octylthiomethyl)-o-cresol, 2,2'-thiobis Ethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-thiobis(4-methyl-6-tert-butyl phenol), 2,2'-thiobis(6-tert-butyl-p-cresol), 2-ethylhexyl-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfur Acetate, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(4-methyl-6-tert-butylphenol) , 4,4'-[thiobis(methylene)]bis(2-tert-butyl-6-methyl-1-hydroxybenzyl), bis(4,6-di-tert-butylphenol -2-yl)sulfide, tridecyl-3,5-di-tert-butyl-4-hydroxybenzylthioacetate, 1,4-bis(octylthiomethyl)-6- Methylphenol, 2,4-bis(dodecylthiomethyl)-6-methylphenol, distearyl-disulfide, bis(methyl-4-[3-n-alkyl(C12 /C14) thiopropionyloxy] 5-tert-butylphenyl) sulfide, etc. These thioether-based antioxidants may be used alone or in combination of two or more.

As other antioxidants, for example, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α - Undecyl nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octyl-α-heptadecane Nitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone Ketones, nitrone compounds such as N-octadecyl-α-heptadecylnitrone, 3-arylbenzofuran-2(3H)-one, 3-(alkoxyphenyl)benzofuran -2-one, 3-(acyloxyphenyl)benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)- Benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-(4-hydroxyphenyl)-benzofuran-2(3H)-one, 5,7-di- Tributyl-3-{4-(2-hydroxyethoxy)phenyl}-benzofuran-2(3H)-one, 6-(2-(4-(5,7-di-tert-butyl Base-2-oxo-2,3-dihydrobenzofuran-3-yl)phenoxy)ethoxy)-6-oxohexyl-6-((6-hydroxyhexyl)oxy) Hexanoate, 5-di-tert-butyl-3-(4-((15-hydroxy-3,6,9,13-tetraoxapentadecyl)oxy)phenyl)benzofuran- Benzofuran compounds such as 2(3H) ketones, etc. These other antioxidants may be used individually by 1 type, and may use 2 or more types together.

Examples of light stabilizers include 2,2,6,6-tetramethyl-4-piperidinyl stearate, 1,2,2,6,6-pentamethyl-4-piperidinyl Stearate, 2,2,6,6-tetramethyl-4-piperidinyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid Esters, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)- 1,2,3,4-butane tetracarboxylate, Tetra(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate ester, bis(2,2,6,6-tetramethyl-4-piperidinyl)‧bis(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1 ,2,2,6,6-pentamethyl-4-piperidinyl)‧bis(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2 ,6,6-pentamethyl-4-piperidinyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2 -Hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl -4-piperidinylamino)hexane/2,4-dichloro-6-morpholinyl-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl -4-piperidinylamino)hexane/2,4-dichloro-6-tertiary octylamino-s-triazine polycondensate, 1,5,8,12-tetra[2,4- Bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazin-6-yl]-1,5,8,12- Tetraazadodecane, 1,5,8,12-tetra[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl )amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-reference [2,4-bis(N-butyl-N -(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-reference[2,4 -bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazin-6-yl]aminoundecane, Bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl)decanedioate, bis(2,2,6,6-tetramethyl-1-deca Monoalkyloxypiperidin-4-yl) carbonate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 1,2,3,4-butanetetracarboxylic acid , a polymer of 2,2-bis(hydroxymethyl)-1,3-propanediol and 3-hydroxy-2,2-dimethylpropanol, 1,2,2,6,6-pentamethyl-4 -piperidinyl ester, 1,3-bis(2,2,6,6-tetramethylpiperidin-4-yl)2,4-di-tridecylbenzene-1,2,3,4- Tetracarboxylate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly[[6-[(1,1,3, 3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imine base]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]), TINUVIN NOR 371 manufactured by BASF Corporation, and the like. These photostabilizers may be used alone or in combination of two or more.

Examples of ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 5,5 2-hydroxybenzophenones such as '-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl)benzotri Azole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl- 5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tertoctylphenyl)benzotriazole, 2-(2'-hydroxy-3' ,5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tertoctyl-6-(benzotriazolyl)phenol), 2-(2 '-Hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole and other 2-(2'-hydroxyphenyl)benzotriazoles; phenyl salicylate, terephthalate Phenol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-pentylbenzene Benzoyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and other benzoates; 2-Ethyl-2'-ethoxyoxalylaniline, 2-ethoxy-4'-dodecyloxalylaniline and other substituted oxalylanilines; ethyl-α-cyano-β , β-diphenyl acrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl) acrylate and other cyanoacrylates; 2-(2-hydroxy-4 -octyloxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4 ,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylbenzene base)-s-triazine and other triaryl triazines. These ultraviolet absorbers may be used alone or in combination of two or more.

Examples of crystal nucleating agents include metal carboxylates such as sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate, and 2-sodium bicyclo[2.2.1]heptane-2,3-dicarboxylate. Salt, sodium bis(4-tert-butylphenyl)phosphate, sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, lithium-2,2' -Phosphate metal salts such as methylene bis(4,6-di-tert-butylphenyl) phosphate, dibenzylidene sorbitol, bis(methylbenzylidene) sorbitol, bis(3, 4-Dimethylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, bis(dimethylbenzylidene)sorbitol, 1,2,3-trideoxy- 4,6:5,7-bis-O-((4-propylphenyl)methylene)-nonanediol, 1,3:2,4-bis(p-methylbenzylidene)sorbose Alcohol, 1,3:2,4-bis-O-benzylidene-D-glucitol (dibenzylidene sorbitol) and other polyol derivatives, N,N',N"-reference [2-methyl Cyclohexyl]-1,2,3-propanetricarboxamide, N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexyl- Amide compounds such as naphthalene dicarboxamide and 1,3,5-tris(dimethylisopropylamino)benzene, etc. These crystal nucleating agents may be used alone or in combination of two or more.

Examples of plasticizers include epoxy systems such as epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl esters, or methacrylates, or polycondensates of dicarboxylic acids and polyhydric alcohols, polycarboxylic acid Polyesters such as polycondensates with polyols, or polycondensates of dicarboxylic acids, polyols, and alkanediols, polycondensates of dicarboxylic acids, polyols, and aromatic diols, polycarboxylic acids, polyols, and Polyether esters such as polycondensates of alkanediol, polycondensates of polycarboxylic acids and polyols and aryl glycols, or aliphatic esters such as adipate and succinate, or phthalates , terephthalate, trimellitate, pyromellitic acid ester, benzoic acid ester and other aromatic esters, etc. These plasticizers may be used alone or in combination of two or more.

Examples of lubricants include liquid paraffin, natural paraffin, microcrystalline wax, synthetic paraffin, low molecular weight polyethylene, polyethylene wax and other pure hydrocarbon lubricants; halogenated hydrocarbon lubricants; fatty acid lubricants such as higher fatty acids and oxygen fatty acids ; Fatty acid amide, bis fatty acid amide and other fatty acid amide-based lubricants; lower alcohol esters of fatty acids, polyol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids (ester wax) and other esters Lubricant; metal soap, fatty alcohol, polyol, polyglycol, polyglycerol, partial ester of fatty acid and polyol, partial ester of fatty acid and polyglycol, polyglycerol, or silicone oil, mineral oil, etc. These lubricants may be used alone or in combination of two or more.

As a flame retardant other than the flame retardant related to the flame retardant composition of the present invention, for example, triphenyl phosphate, tricresyl phosphate, tri-xylyl phosphate, cresyl diphenyl phosphate, methyl Phenyl-2,6-di-xylyl phosphate, catechol bis(diphenyl phosphate), (1-methylethylidene)-4,1-phenylene tetraphenyl diphosphate Esters, 1,3-phenylene tetrakis (2,6-dimethylphenyl) phosphate, ADEKA Co., Ltd. product name "ADEKASTAB FP-500", "ADEKASTAB FP-600", "ADEKASTAB FP- 800", "ADEKASTAB FP-900L" and other aromatic phosphates, phosphonic acid esters such as divinyl phenyl phosphonate, diallyl phenyl phosphonate, (1-butenyl) phenyl phosphonate, di Phenyl phosphonite, methyl diphenyl phosphinate, 9,10-dihydro-9-oxa-10-phosphoranthrene-10-oxide derivatives and other phosphonites, diethyl Dialkylphosphonites such as aluminum phosphonite, zinc diethylphosphonite, etc., phosphazene compounds such as bis(2-allylphenoxy)phosphazene, xylenylphosphazene, etc., inorganic compounds such as red phosphorus Phosphorus flame retardant, magnesium hydroxide, aluminum hydroxide and other metal hydroxides, brominated bisphenol A type epoxy resin, brominated phenol novolak type epoxy resin, hexabromobenzene, pentabromotoluene, ethylidene Bis(pentabromophenyl), ethylidenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane , hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-ginseng(tribromophenoxy)-1,3, 5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A dimethacrylate, pentabromobenzyl acrylate, Brominated phenyl acetylene and other brominated flame retardants, etc. These flame retardants may be used alone or in combination of two or more.

Examples of antistatic agents include cationic antistatic agents such as fatty acid quaternary ammonium ion salts, polyamine quaternary salts, or higher alcohol phosphate ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anion Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, higher alcohol ethylene oxide adduct phosphates, or polyol fatty acids Non-ionic antistatic agents such as esters, polyglycol phosphate esters, polyoxyethylene alkyl allyl ethers, or amphoteric alkyl betaines such as alkyl dimethylaminoacetic acid betaines, imidazoline amphoteric active agents, etc. Amphoteric antistatic agent. These antistatic agents may be used alone or in combination of two or more.

Examples of fillers include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, dolomite Stone, silicon oxide, aluminum oxide, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, montmorillonite, etc. The particle size can be determined by properly selecting the fiber diameter or fiber length and aspect ratio in the fibrous form. use. These fillers may be used alone or in combination of two or more. In addition, as a filler, those subjected to surface treatment as necessary can be used.

Examples of pigments include Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; pigment green 7, 10, 36; pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc. These pigments may be used alone or in combination of two or more.

Examples of dyes include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, Dyes such as base dyes, indamide dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, etc. These dyes may be used alone or in combination of two or more.

In addition, one or more additives selected from the above-mentioned additives, surface treatment agents, dust inhibitors and other components can be formulated in the flame retardant composition of the present invention, and can also be formulated in the composition containing the flame retardant In flame retardant resin compositions of materials and thermoplastic resins.

The flame retardant composition of the present invention is effective for flame retardant of synthetic resins, and is preferably blended with synthetic resins to make flame retardant resin compositions for use.

＜Flame Retardant Resin Composition＞ The flame retardant resin composition of the present invention contains the flame retardant composition of the present invention and a thermoplastic resin. The content of the flame retardant composition of the present invention is usually 10-400 parts by weight, preferably 15-200 parts by weight, more preferably 20-70 parts by weight, relative to 100 parts by weight of the thermoplastic resin. Thereby, the flame retardancy of a thermoplastic resin can be fully improved.

Examples of thermoplastic resins include synthetic resins such as polyolefin-based resins, styrene-based resins, polyester-based resins, polyether-based resins, polycarbonate-based resins, polyamide-based resins, and halogen-containing resins. These may be used alone or in combination of two or more.

Further examples of thermoplastic resins include petroleum resins, coumarone resins, polyvinyl acetate, acrylic resins, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, Thermoplastic resins such as polyphenylene sulfide, polyurethane, cellulose-based resins, polyimide resins, polypropylene, liquid crystal polymers, and blends thereof.

Also, the thermoplastic resin may be isoprene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber , Olefin-based elastomers, Styrene-based elastomers, Polyester-based elastomers, Nitrile-based elastomers, Nylon-based elastomers, Vinyl chloride-based elastomers, Polyamide-based elastomers, Polyurethane-based elastomers Other thermoplastic elastomers can also be used in combination.

Specific examples of thermoplastic resins are not particularly limited, but examples include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polybutene-1, poly-3-methylpentene, poly Polyolefin-based resins such as 4-methylpentene, ethylene/propylene block or random copolymers and other α-olefin polymers; polyethylene terephthalate, polybutylene terephthalate, polyterephthalate Thermoplastic linear polyester resins such as hexamethylene dicarboxylate; polysulfide resins such as polyphenylene sulfide; polylactic acid resins such as polycaprolactone; linear polyamides such as polyhexamethylene adipamide Resins; crystalline polystyrene resins such as syndiotactic polystyrene, etc.

These thermoplastic resins, regardless of molecular weight, degree of polymerization, density, softening point, insoluble ratio to solvents, degree of stereoregularity, presence or absence of catalyst residues, types of monomers used as raw materials, and blending ratios, such as Ziegler catalysts, Any kind of polymerization catalyst such as a metallocene catalyst can be used. Among these thermoplastic resins, from the viewpoint of imparting excellent flame retardancy, one or more selected from the group consisting of polyolefin resins, polystyrene resins, and copolymers thereof are preferred, and polymers are more preferred. The olefin-based resin is more preferably polypropylene, high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, and it is also preferable to use these together with a thermoplastic elastomer.

The flame retardant resin composition of the present invention preferably contains glass fibers. Thereby, resin physical properties and flame retardancy can be improved.

The type of glass fiber is not particularly limited, and E glass, C glass, S glass, D glass, etc. can be used, and the shape is not particularly limited, and any glass fiber such as chopped fibers, rovings, yarns, glass wool, etc. can also be used . A commercially available glass fiber can also be used.

Glass fibers are preferably chopped fibers in which single fibers are bundled in terms of processability and flame retardancy. When chopped fibers are used, the cut length is preferably 0.5 mm to 10 mm, more preferably 2 mm to 5 mm, based on processability and flame retardancy. In addition, the single fiber diameter is preferably 8 μm to 20 μm, more preferably 10 μm to 15 μm, in terms of processability and flame retardancy.

Glass fibers can be treated with surface treatment agents in order to have good wettability and adhesion with thermoplastic resins. Examples of surface treatment agents include silane-based, titanate-based, aluminum-based, chromium-based, zirconium-based, and borane-based coupling agents. Among them, silane-based coupling agents and titanate-based coupling agents are preferred. , particularly preferably a silane-based coupling agent. As the silane-based coupling agent, for example, triethoxysilane, vinyl ginseng (β-methoxyethoxy) silane, γ-methacryloxypropyl trimethoxysilane, γ-shrink Glyceryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxy Silane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc.

Glass fiber can also use a bundler to bundle the glass fiber. As a constricting agent, a polypropylene resin, a polyurethane resin, a polyester resin, an acrylic resin, an epoxy resin, starch, vegetable oil, etc. are mentioned, for example.

The glass fiber content in the flame retardant resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of the total mass of the flame retardant resin composition. Preferably it is 5-40 mass parts, More preferably, it is 10-30 mass parts.

The flame retardant resin composition of the present invention, in addition to the flame retardant composition of the present invention, may also contain one of the additives selected from the above-mentioned auxiliary agents, surface treatment agents, dust inhibitors and other components. more than one species. These may be used alone or in combination of two or more.

The content of the filler in the flame retardant resin composition of the present invention and the additives other than the flame retardant related to the flame retardant composition of the present invention is, for example, 0.001 to 15 parts by weight relative to 100 parts by weight of the thermoplastic resin. Preferably it is 0.005-10 parts by weight, more preferably 0.01-5 parts by weight. By setting it as this numerical range, the improvement of the additive effect can be acquired.

In the flame retardant resin composition of the present invention, the content of the filler when blended is, for example, 1 to 100 parts by mass, preferably 3 to 80 parts by mass, more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the thermoplastic resin share.

In the flame retardant resin composition of the present invention, the content of the flame retardant other than the flame retardant related to the flame retardant composition of the present invention is, for example, 1 to 200 parts by mass relative to 100 parts by mass of the thermoplastic resin. Preferably it is 3-150 mass parts, More preferably, it is 5-80 mass parts.

When the flame retardant resin composition of the present invention uses a polyolefin resin or an olefin elastomer as a thermoplastic resin, in order to neutralize the catalyst residue in the resin, it is preferable to contain conventional Know the neutralizer. As the neutralizing agent, for example, fatty acid metal salts such as calcium stearate, lithium stearate, sodium stearate, magnesium stearate, etc., ethylidene bis(stearyl amide), ethylidene bis( 12-hydroxy stearic acid amide), fatty acid amide compounds such as stearic acid amide, or inorganic compounds such as hydrotalcite. These neutralizing agents may be used alone or in combination of two or more. The amount of these neutralizing agents is preferably 0.001-3 parts by mass, more preferably 0.01-1 part by mass, relative to 100 parts by mass of the thermoplastic resin.

When glass fibers are contained in the flame retardant resin composition of the present invention, it is preferable to contain a compatibilizing agent within the range that does not impair the effects of the present invention in order to improve the compatibility between the resin and the glass fibers. As a compatibilizing agent, the modified resin etc. which have affinity to both base resin and glass fiber are mentioned, for example. As an example of a compatibilizing agent, when the base resin is a polyolefin resin, maleic anhydride-modified polyolefins such as maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene, and silane-modified polyolefins are exemplified. Among them, maleic anhydride-modified polyolefin is preferred. These compatibilizing agents may be used alone or in combination of two or more. The amount of these compatibilizers used is preferably 0.1-30 parts by mass, more preferably 0.5-20 parts by mass, and even more preferably 1-15 parts by mass relative to 100 parts by mass of glass fiber .

Next, the manufacturing method of the flame-retardant resin composition of this invention is demonstrated. The flame retardant resin composition of the present invention can be obtained by mixing the flame retardant composition of the present invention with a thermoplastic resin. The above-mentioned additives may also be mixed as needed. The additives can be mixed in the flame retardant composition, and can also be mixed in the mixture of the flame retardant composition and the thermoplastic resin.

As a hybrid method, a generally used conventional method can be directly applied. For example, a method of mixing a flame retardant composition, a thermoplastic resin, and additives as necessary with a mixer such as a general blender or mixer, a method of melting and kneading with an extruder, or a method of casting a solution mixed with a solvent wait.

The flame retardant resin composition of the present invention can be used in various forms, for example, any of tablet form, granular form, and powder form. From the viewpoint of handleability, it is preferably in the form of pellets.

＜Molded products＞ Molded articles can be manufactured by molding using the flame retardant resin composition of the present invention. The molding method is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, expansion molding, calender molding, cable-drawing molding, dip molding, hair molding, etc. Bubble forming method, additive manufacturing method, etc. Among these, injection molding, extrusion molding, and blow molding are preferable. Thereby, molded products of various shapes such as resin plates, sheets, films, irregular products, etc. can be produced.

Molded articles using the flame retardant resin composition of the present invention can be used in various applications, such as electrical and electronic parts, mechanical parts, optical equipment, building components, automobile parts, and daily necessities. Among them, from the viewpoint of flame retardancy, it can be suitably used for electrical and electronic parts and building components.

The flame retardant resin composition of the present invention and its molded products can be used in, for example, electrical, electronic, and communication, agriculture, forestry and fishery, mining, construction, food, fiber, clothing, medical treatment, coal, petroleum, rubber, leather, automobile, precision instrument , wood, building materials, civil engineering, furniture, printing, musical instruments, etc. Specifically, the flame retardant resin composition of the present invention and its molded products can be used in printers, personal computers, word processors, keyboards, PDAs (miniature information terminals), telephones, photocopiers, facsimile machines, ECR ( Electronic currency registration machine), computers, electronic notebooks, cards, brackets, stationery, etc., OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting appliances, game consoles, irons, kiosks and other home appliances, TV, VTR, Video recorders, recorders, tape recorders, mini discs, CD players, speakers, liquid crystal displays and other AV equipment, connectors, relays, capacitors, switches, printed circuit boards, bobbins, semiconductor sealing materials, LED sealing materials Electrical and electronic components such as wires, cables, transformers, deflectors, switchboards, clocks, etc., and communication equipment, etc.

The flame retardant resin composition of the present invention and its molded products can be used in, for example, seats (fillers, surface fabrics, etc.), belts, ceilings, liftable top panels, armrests, door trims, trunk partitions, carpets, Mats, sun visors, rim covers, bedspreads, airbags, insulating materials, rings, ring straps, wire covering materials, electrical insulating materials, paints, coating materials, flooring materials, flooring materials, corners, carpets, wallpapers, Wall cladding, exterior cladding, interior cladding, roofing, decking, walling, columns, flooring, fencing, framing and moldings, window and door frames, shingles, siding, terraces, balconies, soundproofing panels Materials for automobiles, vehicles, ships, airplanes, buildings, houses, etc., building materials or civil engineering materials, clothing materials, curtains, bed sheets, plywood, synthetic fiberboards, carpets, entrance mats, boards, etc. , barrels, hoses, containers, glasses, leather bags, casings, goggles, skis, rackets, tents, musical instruments, etc. daily necessities, sports goods, etc.

As mentioned above, although the embodiment of this invention was described, these are illustrations of this invention, and various structures other than these can be employ|adopted. In addition, the present invention is not limited to the above-mentioned embodiments, and modifications, improvements, and the like within the scope of attaining the object of the present invention are included in the present invention. [Example]

The reference examples of the present invention will be described in detail below, but the present invention is by no means limited to the descriptions of these examples.

[Examples 1-16, Comparative Examples 1-10] The details of each component in Tables 1 to 7 are shown below. (a1) Melamine salt: The following manufacturer was used. (a2) Piperazine salt: The following manufacturer was used. (B) Stearic acid: trade name BEADS STEARIC ACID CHERRY, manufactured by NOF, melting point 60°C (B) Calcium stearate: trade name Calcium Stearate, manufactured by Dannan Chemical Industry, melting point 160°C (B) Zinc stearate: trade name Zinc Stearate TM, manufactured by Faci Asia Pacific, melting point 118~122°C (C) Kaolin: trade name GLOWMAX LL, manufactured by IMERYS (C) Talc: trade name MICRO ACE P-4, made in Japan talc Polypropylene (1): impact copolymer polypropylene, trade name PRIME POLYPRO J-754HP, manufactured by PRIME Polymers Co., Ltd., melt flow rate (according to JIS K7210, load 2.16 kg, temperature 230° C.) = 14 g/10 min Polypropylene (2): impact copolymer polypropylene, trade name PRIME POLYPRO J-707G, manufactured by PRIME Polymers Co., Ltd., melt flow rate (according to JIS K7210, load 2.16 kg, temperature 230° C.) = 30 g/10 min Phenolic antioxidant: tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate methyl ester] methane, trade name DAEKASTAB AO-60, manufactured by ADEKA Phosphorus-based antioxidant: ginseng (2,4-di-tert-butylphenyl) phosphite, trade name ADEKASTAB 2112, manufactured by ADEKA Neutralizer: calcium stearate, trade name Calcium Stearate, manufactured by Tannam Chemical Industry Maleic acid modified polypropylene: Maleic anhydride modified polypropylene, trade name UMEX1010, manufactured by Sanyo Chemical Industry Glass fiber: chopped fiber, trade name CSF3PE-957S, manufactured by Nitto Industries, cut length 3.0 mm, single fiber diameter 13 μm

＜Ingredient (a1): Manufacture of melamine salt＞ Melamine orthophosphate was heated and condensed in a solid state at 220°C for 6 hours to produce melamine salt with melamine pyrophosphate as the main component. The melamine salt was used directly without purification. The purity of melamine pyrophosphate in melamine salt is 98.5%.

＜Component (a2): Manufacture of piperazine salt＞ Piperazine diphosphate is heated and condensed in a solid state at 250°C for 1 hour to produce piperazine salt with piperazine pyrophosphate as the main component. The piperazine salt was used without purification. The purity of piperazine pyrophosphate in piperazine salt is 99.0%.

The purity of the obtained melamine salts and piperazine salts was determined using an ion chromatography measuring device ICS-2100 (Thermo Fisher Scientific Co., Ltd.), a Dionex IonPac AS-19 column (Thermo Fisher Scientific Co., Ltd.), and a conductivity detector. .

＜Manufacture of flame retardant compositions A1~A5, A10~A13＞ Weigh each component according to the formulation described in Table 1 and Table 2, and use a Henschel mixer (FM100, manufactured by Mitsui Mining Co., Ltd.) to mix for 10 minutes at a rotation speed of 850 rpm and a tank temperature of 80°C to obtain a surface-treated mixture. Fuel composition A1~A5, A10~A13. In addition, the compounding quantity unit in a table|surface is a mass part.

＜Manufacture of Flame Retardant Compositions A6~A7＞ Except that the formulation and weighing of each component described in Table 1 and Table 2, and the temperature in the tank of the Henschel mixer was set to 165°C, the production procedure was the same as that of the flame retardant composition A1 to obtain the surface-treated Flame retardant composition A6~A7. In addition, the compounding quantity unit in a table|surface is a mass part.

＜Manufacture of Flame Retardant Compositions A8~A9＞ Except for weighing each component according to the formulation described in Table 2, and setting the temperature in the tank of the Henschel mixer to 150°C, the production procedure of the flame retardant composition A1 was the same to obtain a surface-treated flame retardant Composition A8~A9.

＜Manufacture of Flame Retardant Compositions B1~B5＞ Except that the preparation and weighing of each component described in Table 3 was carried out, and the temperature in the tank of the Henschel mixer was set at 25°C, the production procedure of the flame retardant composition A1 was the same as that of the flame retardant composition A1 to obtain the flame retardant composition B1~ B5. In addition, the compounding quantity unit in a table|surface is a mass part.

＜Measurement of electrical conductivity EC＞ With 100mL of ultrapure water, mix 1g of the obtained flame retardant composition (A1~A13, B1~B5) in a 200mL beaker as a sample, and use a magnetic stirring bar (trade name HS-360, manufactured by AS ONE) at 240~300rpm , After stirring for 5 minutes at room temperature of 25°C, place it in a constant temperature water bath at 30°C for 5 minutes, and use it as a measurement solution. With respect to the obtained measurement solution, the conductivity EC was measured using a conductivity meter (EC tester DiST3, manufactured by Hanna).

＜Manufacture of flame retardant resin composition＞ In addition to the obtained flame retardant composition, the flame retardant composition (A1~A13, B1 ~B5), obtain the flame retardant resin composition. In addition, the unit of the compounding quantity in the table is a mass part.

＜Flame resistance evaluation: Oxygen index＞ The resulting flame retardant resin composition was melted and kneaded with a twin-screw extruder (TEX25αIII, manufactured by Nippon Steel Works) at a cylinder temperature of 180-230°C and a screw speed of 150 rpm to obtain pellets of the flame retardant resin composition. The obtained pellets were injection-molded with an injection molding machine (EC60NII-1.5A, manufactured by Toshiba Machinery), and a test piece of 80 mm×10 mm×4 mm was obtained. Using this test piece, evaluation of the oxygen index (%) was performed. In addition, the oxygen index in this specification refers to the minimum oxygen concentration at which a test piece is placed vertically in a mixed gas of nitrogen and oxygen to maintain combustion, and refers to a value measured in accordance with JIS K7201-2. The larger the numerical value, the more excellent the flame retardancy. The measurement results are shown in Tables 4-7.

<Evaluation of Flame Retardancy: Calorific value, Smoke Density (Cone Calorimeter)> The obtained flame retardant resin composition was press-molded at 220° C. to obtain a test piece of 100 mm×100 mm×3 mm. Using the obtained test piece and a cone gauge (CONE III, manufactured by Toyo Seiki Seisakusho Co., Ltd.), according to ISO5660, a heat flow of 50kW/ ^m2 was applied to the test piece to conduct a combustion test, and the total calorific value and smoke density were measured from the start of the test to 600 seconds. Determination. The measurement results are shown in Table 7.

It turns out that Examples 1-9 showed higher oxygen index than Comparative Examples 1-5, and showed high flame retardancy. Moreover, even when glass fibers are blended, the oxygen indices of Examples 10-11 are still higher than those of Comparative Examples 6-8.

Compared with Comparative Examples 9-10, Examples 12-16 have a higher oxygen index, and furthermore, the total calorific value and smoke density during combustion are suppressed, and it can be seen that the flame retardancy and fire safety are higher. The above shows that the flame retardant resin composition using the flame retardant composition of the present invention has high flame retardancy and high safety in the event of fire.

Claims (12)

A flame retardant composition characterized by comprising: (A) component: at least one compound selected from the group consisting of polyphosphate compounds and orthophosphate compounds, and (B) component: selected from fatty acids and fatty acid metals At least one compound of the salt group, when the electrical conductivity of a mixture of 100 parts by mass of ultrapure water and 1 part by mass of the aforementioned flame retardant composition is EC (μS/cm), EC satisfies the following formula ( I),

. The flame retardant composition according to claim 1, wherein the aforementioned component (A) is surface-treated by the aforementioned component (B). The flame retardant composition according to claim 1 or 2, wherein the aforementioned (A) component is one or more selected from the group consisting of the following (a1) component and the following (a2) component, (a1) component: the following The compound represented by general formula (1)

In the general formula (1), n1 represents a number from 1 to 100, ^X1 represents ammonia or a triazine derivative represented by the following general formula (1-A), and p represents a number satisfying 0<p≦n1+2

In the general formula (1-A), Z ¹ and Z ² each independently represent a group selected from -NR ¹¹ R ¹² groups, hydroxyl groups, mercapto groups, linear or branched alkyl groups with 1 to 10 carbon atoms, and alkyl groups with 1 to 10 carbon atoms. 10 Any one of the group of straight-chain or branched alkoxy, phenyl and vinyl groups, ^R11 and ^R12 each independently represent a hydrogen atom, straight-chain or branched alkyl group with 1 to 6 carbon atoms or hydroxymethyl group, (a2) component: a compound represented by the following general formula (2)

In general formula (2), n2 represents a number from 1 to 100, Y ¹ represents [R ²¹ R ²² N(CH ₂ ) _m NR ²³ R ²⁴ ], piperazine or diamine containing a piperazine ring, R ²¹ , R ^22. R ²³ and R ²⁴ each independently represent a hydrogen atom, or a linear or branched alkyl group with 1 to 5 carbon atoms, m is an integer from 1 to 10, and q represents a number satisfying 0<q≦n2+2. The flame retardant composition according to any one of claims 1 to 3, wherein the aforementioned component (B) is a compound represented by the following general formula (3),

In the general formula (3), R ³¹ represents the residue of removing the carboxyl group from a fatty acid with 10 to 30 carbon atoms, and M ¹ represents hydrogen, lithium, sodium, potassium, magnesium, calcium, barium, zinc or Al(OH) _{3- r} , r represents an integer from 1 to 3. The flame retardant composition according to claim 4, wherein the aforementioned (B) component includes M in the general formula (3) and is ^one or more compounds selected from hydrogen and calcium. The flame retardant composition according to any one of Claims 3 to 5, wherein the aforementioned component (A) includes component (a1) in which X ¹ is melamine in the general formula (1). The flame retardant composition according to any one of claims 3 to 5, wherein the aforementioned component (A) includes component (a2) in which Y ¹ is piperazine in the general formula (2). The flame retardant composition according to any one of claims 3 to 7, wherein the aforementioned (A) component comprises: In the general formula (1), n1 is the component (a1) of 2, and In the general formula (2), n2 is the (a2) component of 2. The flame retardant composition according to any one of claims 1 to 8, which further contains 1 to 30 parts by mass of component (C) relative to the total of 100 parts by mass of component (A) and component (B): silicate compound. A flame retardant resin composition, characterized by containing the flame retardant composition according to any one of claims 1 to 9, and thermoplastic resin. The flame retardant resin composition according to claim 10, which further contains glass fibers. A molded article characterized by using the flame retardant resin composition as claimed in claim 10 or 11.