阅读说明：本技术 阻燃剂组合物和阻燃性合成树脂组合物 (Flame retardant composition and flame-retardant synthetic resin composition ) 是由 樱井久史 米泽丰 丹治直子 于 2020-03-19 设计创作，主要内容包括：本发明提供：即使为较少的添加量也能对合成树脂赋予优异的阻燃性的阻燃剂组合物、及含有该阻燃剂组合物和树脂且发挥优异的阻燃性的阻燃性合成树脂组合物。该阻燃剂组合物含有下述(A)成分和下述(B)成分,(A)成分：磷酸盐系阻燃剂,(B)成分：在结构中具有下述化学式(1)所示的结构的受阻胺化合物,上述化学式(1)中的*表示原子键,上述化学式(1)所示的结构任选1个或多个存在于化合物中。(The present invention provides: flame retardant composition capable of imparting excellent flame retardancy to synthetic resin even in a small amount of addition, and flame-retardant synthetic resin composition containing the flame retardant composition and resin and exhibiting excellent flame retardancy. The flame retardant composition comprises the following component (A) and the following component (B): a phosphate flame retardant, and (B) a component: a hindered amine compound having a structure represented by the following chemical formula (1) in the structure, wherein x in the chemical formula (1) represents an atomic bond, and 1 or more structures represented by the chemical formula (1) are optionally present in the compound.)

1. A flame retardant composition comprising the following component (A) and the following component (B),

(A) the components: phosphate flame retardant

(B) The components: a hindered amine compound having a structure represented by the following chemical formula (1),

in the chemical formula (1), x represents an atomic bond, and 1 or more of the structures represented by the chemical formula (1) are optionally present in the compound.

2. The flame retardant composition according to claim 1, wherein the component (B) has a structure represented by the following general formula (2):

in the general formula (2), x represents an atomic bond, n represents an integer of 1 to 100, and R represents¹Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, a hydroxyalkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an oxygen radical, and the alkyl group, the alkoxy group, the hydroxyalkyl group, the hydroxyalkoxy group and the alkenyl group are optionally interrupted by one or more oxygen atoms or carbonyl groups.

3. The flame retardant composition according to claim 1, wherein the component (A) contains the following component (A-1) and/or component (A-2),

(A-1) component: more than 1 melamine salt selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate,

(A-2) component: 1 or more piperazine salts selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate.

4. The flame retardant composition according to claim 1, wherein a content ratio of the (a) component to the (B) component is 99: 1-80: 20, or more.

5. A flame-retardant synthetic resin composition characterized by comprising the flame retardant composition according to claim 1 in a synthetic resin.

6. The flame-retardant resin composition according to claim 5, wherein the synthetic resin is a polyolefin resin.

7. A molded article obtained by molding the flame-retardant synthetic resin composition according to claim 5.

Technical Field

The present invention relates to: a flame retardant composition containing a phosphate flame retardant and a hindered amine compound having a specific structure, and a flame-retardant synthetic resin composition (hereinafter also simply referred to as "resin composition") containing the flame retardant composition.

Background

Synthetic resins have been widely used for building materials, automobile parts, packaging materials, agricultural materials, housing materials for home electric appliances, toys, and the like because of their excellent chemical and mechanical properties. However, most synthetic resins are flammable substances, and it is essential to make them flame retardant depending on the application. In particular, synthetic resins having high flammability, represented by polyolefin resins, are used in a wide range of fields, and therefore, in order to impart flame retardancy to these resins, compounding of a flame retardant is indispensable.

As a method for imparting flame retardancy to synthetic resins, there have been known methods using a halogen-based flame retardant, an inorganic phosphorus-based flame retardant represented by a polyphosphoric acid-based flame retardant such as red phosphorus and ammonium polyphosphate, an organic phosphorus-based flame retardant represented by a triaryl phosphate compound, a metal hydroxide such as magnesium hydroxide, antimony oxide as a flame retardant aid, and a melamine compound, either singly or in combination. However, the halogen-based flame retardant has a problem that harmful gas is generated during combustion. Further, since flame retardancy is not obtained unless a large amount of the metal hydroxide is blended, there is a problem that processability of the resin and physical properties of a molded article are deteriorated. Therefore, as a flame retardant that does not cause such a problem, use of a phosphorus flame retardant has been attempted.

For example, patent document 1 discloses a flame-retardant resin composition containing ammonium polyphosphate, a polyhydric hydroxyl group-containing compound, a triazine ring-containing compound, and a metal hydroxide. Patent documents 2 and 3 disclose flame-retardant synthetic resin compositions containing melamine polyphosphate and pentaerythritol to tripentaerythritol.

Among these, Intumescent flame retardants, which are flame retardants that exhibit flame retardancy by forming a surface Intumescent layer (Intumescent) during combustion and thereby inhibiting diffusion of decomposition products and heat transfer, have excellent flame retardancy. A technique relating to such a flame retardant is described in patent document 4, for example.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 8-176343

Patent document 2: U.S. Pat. No. 3936416 publication

Patent document 3: U.S. Pat. No. 4010137 publication

Patent document 4: japanese patent laid-open publication No. 2003-26935

Disclosure of Invention

Problems to be solved by the invention

However, these conventional phosphate flame retardants have a problem that they have a bad influence on the original physical properties of the resin and increase the blending cost because they need to be added in a large amount in order to impart sufficient flame retardancy to the synthetic resin. Therefore, a flame retardant that exhibits excellent flame retardancy with a smaller amount of addition is required.

Accordingly, an object of the present invention is to provide: a flame retardant composition which can impart excellent flame retardancy to a synthetic resin even when added in a small amount, and a flame-retardant synthetic resin composition which contains the flame retardant composition and a resin and exhibits excellent flame retardancy.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the above object can be achieved by preparing a flame retardant composition containing a phosphate flame retardant and a hindered amine compound having a specific structure, and the present invention has been completed.

That is, the present invention provides a flame retardant composition comprising the following component (A) and the following component (B),

(A) the components: phosphate flame retardant

(B) The components: a hindered amine compound having a structure represented by the following chemical formula (1),

in the above chemical formula (1), a indicates an atomic bond, and 1 or more of the structures represented by the above chemical formula (1) are optionally present in the compound.

In the flame retardant composition of the present invention, the component (B) preferably has a structure represented by the following general formula (2):

in the general formula (2), x represents an atomic bond, n represents an integer of 1 to 100, and R¹Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, a hydroxyalkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an oxygen radical, and the alkyl group, the alkoxy group, the hydroxyalkyl group, the hydroxyalkoxy group and the alkenyl group are optionally interrupted by one or more oxygen atoms or carbonyl groups.

In the flame retardant composition of the present invention, the component (A) preferably contains the following component (A-1) and/or component (A-2),

(A-1) component: 1 or more melamine salts selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate

(A-2) component: 1 or more piperazine salts selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate

Further, in the flame retardant composition of the present invention, the content ratio of the component (a) to the component (B) is preferably 99: 1-80: 20, or more.

The present invention also provides a flame-retardant synthetic resin composition, which is characterized in that the flame retardant composition is blended with a synthetic resin.

In the flame-retardant synthetic resin composition of the present invention, the synthetic resin is preferably a polyolefin resin.

Further, the present invention provides a molded article obtained by molding the flame-retardant synthetic resin composition.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a flame retardant composition which can impart flame retardancy more excellent than ever to a synthetic resin can be provided. Further, according to the present invention, a flame-retardant synthetic resin composition excellent in flame retardancy can be provided. Further, according to the present invention, a molded article having excellent flame retardancy can be provided.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail.

The flame retardant composition of the present invention contains the following components (a) and (B):

(A) the components: phosphate flame retardant

(B) The components: a hindered amine compound having a structure represented by the following chemical formula (1)

In the above chemical formula (1), a indicates an atomic bond, and 1 or more of the structures represented by the above chemical formula (1) are optionally present in the compound.

In the flame retardant composition of the present invention, the phosphate flame retardant used as the component (a) contains phosphoric acid.

The phosphoric acid compound used for the phosphate flame retardant is not particularly limited, and various phosphoric acid compounds such as orthophosphoric acid, pyrophosphoric acid, and polyphosphoric acid may be mentioned.

Examples of the phosphate flame retardant include phosphates containing salts of the above-mentioned various phosphoric acids and at least one metal or compound selected from the group consisting of metals of groups 1 to 14 of the periodic table, ammonia, aliphatic amines, and aromatic amines.

Examples of the metal of group 1 to group 14 of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), aluminum, and the like.

Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine.

Examples of the aromatic amine include pyridine, pyrazine, pyridazine, pyrimidine, triazine, melamine, melam, and melem.

The phosphate flame retardant may be subjected to a known water resistance-improving treatment such as a silane coupling agent treatment or a coating with a melamine resin, or may be added with a known foaming aid such as melamine, melamine cyanurate, or pentaerythritol.

Specific examples of the phosphate flame retardant include orthophosphates, pyrophosphates, and polyphosphates.

The orthophosphates are not particularly limited, and examples thereof include ammonium salts such as ammonium phosphate, monoammonium phosphate and diammonium phosphate, sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite and sodium hypophosphite, potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite and potassium hypophosphite, lithium salts such as monopotassium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite and lithium hypophosphite, barium salts such as barium dihydrogenphosphate, barium hydrogenphosphate, tribasic barium hypophosphite and barium hypophosphite, magnesium salts such as magnesium monohydrogenphosphate, magnesium hydrogenphosphate, trimagnesium phosphate and magnesium hypophosphite, calcium salts such as calcium dihydrogenphosphate, calcium hydrogenphosphate, tricalcium phosphate and calcium hypophosphite, zinc salts such as zinc phosphate, zinc hypophosphite and the like, amine salts such as piperazine phosphate and melamine phosphate, and the like.

The pyrophosphate is not particularly limited, and examples thereof include ammonium pyrophosphate, piperazine pyrophosphate, melamine pyrophosphate, and aluminum pyrophosphate.

The polyphosphate salt is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, and aluminum polyphosphate.

The phosphate flame retardant may be used in a mixture of 1 or 2 or more.

The phosphate flame retardant as the component (A) preferably contains the following component (A-1) and/or component (A-2) from the viewpoint of flame retardancy and heat resistance,

(A-1) component: 1 or more melamine salts selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate

(A-2) component: 1 or more piperazine salts selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate

In the component (a) of the present invention, the melamine salt used as the component (a-1) is selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate, which may be used alone or in a mixture. Among these, melamine pyrophosphate is preferable from the viewpoint of flame retardancy, handling properties and storage stability. When these are used in a mixture, the higher the content of melamine pyrophosphate, the more preferable. In addition, the ratio of pyrophosphoric acid to melamine in melamine pyrophosphate is preferably 1: 2.

the salts of these phosphoric acids and melamine can also be obtained by reacting the corresponding phosphoric acids or phosphoric acids with melamine, but the melamine salt used as the component (a-1) in the present invention is preferably melamine pyrophosphate or melamine polyphosphate obtained by heat condensation of melamine orthophosphate, and particularly preferably melamine pyrophosphate.

In the component (a) of the present invention, the piperazine salt used as the component (a-2) is selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate, and these may be used alone or in a mixture. Of these, piperazine pyrophosphate is preferable from the viewpoint of flame retardancy, handleability, and storage stability, and when used as a mixture, the higher the content of piperazine pyrophosphate is, the more preferable. In addition, the molar ratio of pyrophosphate to piperazine in piperazine pyrophosphate is preferably 1: 1.

the salts of these phosphoric acids and piperazine can also be obtained by reacting piperazine with the corresponding phosphoric acids or phosphoric acid salts, but the piperazine salt used as the component (a-2) in the present invention is preferably piperazine pyrophosphate or piperazine polyphosphate obtained by heat-condensing 1-piperazine-2-orthophosphoric acid, and particularly preferably piperazine pyrophosphate.

When the component (A) of the present invention contains the components (A-1) and (A-2), the content ratio of the component (A-1) to the component (A-2) is preferably 20: 80-50: from the viewpoint of flame retardancy, 50 is more preferably 30: 70-45: 55.

the component (B) of the present invention is a hindered amine compound having a structure represented by the following chemical formula (1) in its structure.

In the above chemical formula (1), a indicates an atomic bond, and 1 or more of the structures represented by the above chemical formula (1) are optionally present in the compound.

Further, as the component (B), a compound having a structure represented by the following general formula (3) is more preferable from the viewpoint of thermal stability, coloring resistance and heat-resistant coloring resistance.

In the above chemical formula (3), R represents an atomic bond¹Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, a hydroxyalkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an oxygen radical, the alkyl group, the alkoxy group, the hydroxyalkyl group, the hydroxyalkoxy group and the alkenyl group being optionally substituted by one or more oxygen atoms or oxygen radicalsThe carbonyl group is interrupted. In addition, 1 or more structures represented by the above general formula (3) are optionally present in the compound.

As R in the above general formula (3)¹Examples of the alkyl group having 1 to 30 carbon atoms which can be used include a straight-chain alkyl group and a branched-chain alkyl group. Examples of the linear alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups. Examples of the branched alkyl group include those in which 1 or 2 or more of the above-mentioned linear alkyl groups are substituted with an alkyl group having 1 to 9 carbon atoms.

R as the above general formula (3)¹Examples of the alkoxy group having 1 to 30 carbon atoms which may be used include alkoxy groups corresponding to the above alkyl groups.

R as the above general formula (3)¹Examples of the hydroxyalkyl group having 1 to 30 carbon atoms which can be used include hydroxyalkyl groups corresponding to the above-mentioned alkyl groups.

R as the above general formula (3)¹Examples of the hydroxyalkoxy group having 1 to 30 carbon atoms which can be used include hydroxyalkoxy groups corresponding to the above alkoxy groups.

R as the above general formula (3)¹Examples of the alkenyl group having 2 to 30 carbon atoms which may be used include an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, an eicosenyl group, a heneicosenyl group, a docosenyl group, a tricosenyl group, a tetracosenyl group, a pentacosenyl group, a hexacosenyl group, a heptacosenyl group, an octacosenyl group, a nonacosenyl group, and a triacontenyl group, and also include an alkadienyl group and an alkatrienyl group.

As mentioned aboveThe structure represented by the general formula (3) R is represented by the formula R in view of thermal stability, discoloration resistance and heat-resistant discoloration resistance¹Preferably an alkyl group having 1 to 30 carbon atoms or a hydrogen atom, more preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and most preferably a methyl group or a hydrogen atom.

The hindered amine compound of component (B) preferably has a structure represented by the following general formula (2) in view of thermal stability, resistance to coloration, and resistance to thermal coloration.

In the general formula (2), x represents an atomic bond, and n represents an integer of 1 to 100. In addition, for R in the above general formula (2)¹Examples of R in the above general formula (3) include¹As exemplified.

The structure represented by the general formula (2) R is R in terms of thermal stability, discoloration resistance and heat-resistant discoloration resistance¹Preferably an alkyl group having 1 to 30 carbon atoms or a hydrogen atom, more preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and most preferably a methyl group or a hydrogen atom.

The component (B) of the present invention may be used in 1 kind or 2 or more kinds.

Specific examples of the component (B) of the present invention include ADK STAB LA-63P (manufactured by ADEKA Co., Ltd.), and ADK STAB LA-68 (manufactured by ADEKA Co., Ltd.).

The content ratio of the component (a) to the component (B) in the flame retardant composition of the present invention is preferably 99: 1-80: 20, more preferably 97: 3-84: 16, or more.

In the flame retardant composition of the present invention, an anti-dripping agent may be added as needed within a range not impairing the effects of the present invention. The anti-dripping agent includes a fluorine-based anti-dripping agent, silicone rubbers, and layered silicates.

Examples of the layered silicate include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, and nontronite, vermiculite, halloysite, swellable mica, and talc, and organic cations, quaternary ammonium cations, and phosphonium cations may be intercalated between the layers.

The anti-dripping agent is particularly preferably a fluorine-based anti-dripping agent, and specific examples of the fluorine-based anti-dripping agent include fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride and polyhexafluoropropylene, alkali metal perfluoroalkanesulfonates such as sodium perfluoromethane sulfonate, potassium perfluoron-butane sulfonate, potassium perfluorot-butane sulfonate, sodium perfluorooctanesulfonate and calcium perfluoro-2-ethylhexane sulfonate, and alkaline earth metal perfluoroalkanesulfonates. Among the anti-dripping agents, polytetrafluoroethylene is most preferable from the viewpoint of anti-dripping properties.

When the flame retardant composition of the present invention contains an antidrip agent, the content of the antidrip agent is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 5 parts by mass, particularly preferably 0.05 to 3 parts by mass, and particularly preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total of the components (a) and (B). If the amount is less than 0.005 part by mass, the drip-proof effect may be insufficient, and if the amount exceeds 5 parts by mass, the properties of the resin may be deteriorated.

In the flame retardant composition of the present invention, a silicone oil may be blended as necessary in order to suppress secondary aggregation at the time of blending and improve water resistance, within a range not impairing the effects of the present invention. Examples of the silicone oil include a side chain of polysiloxane, a dimethyl silicone oil having all methyl groups at the terminal, a methylphenyl silicone oil having a part of the side chain of polysiloxane as a phenyl group, a methylhydrogen silicone oil having a part of the side chain of polysiloxane as a hydrogen group, and copolymers thereof, and further: modified silicone oils obtained by introducing an organic group into a part of the side chain and/or end of the silicone oil, such as 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.

Specific examples of commercially available products of the silicone oils include KF-96 (manufactured by shin-Etsu chemical Co., Ltd.), KF-965 (manufactured by shin-Etsu chemical Co., Ltd.), KF-968 (manufactured by shin-Etsu chemical Co., Ltd.), and the like as the dimethylsilicone oil or the silicone oil having a methylhydrogenpolysiloxane structure, KF-99 (manufactured by shin-Etsu chemical Co., Ltd.), KF-9901 (manufactured by shin-Etsu chemical Co., Ltd.), HMS-151 (manufactured by Gelest Co., Ltd.), HMS-071 (manufactured by Gelest Co., Ltd.), HMS-301 (manufactured by Gelest Co., Ltd.), DMS-H21 (manufactured by Gelest Co., Ltd.), and examples of the methylphenyl silicone oil include KF-50 (manufactured by shin chemical Co., Ltd.), KF-53 (manufactured by shin-Etsu chemical Co., Ltd.), KF-54 (manufactured by shin chemical Co., Ltd.), and the like, KF-56 (manufactured by shin-Etsu chemical Co., Ltd.), examples of the epoxy-modified product include 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.), examples of the carboxyl-modified product include X-22-3701E (manufactured by shin-Etsu chemical Co., Ltd.), examples of the methanol-modified product include X-22-4039 (manufactured by shin-Etsu chemical Co., Ltd.), and examples of the X-22-4015 (manufactured by shin-Etsu chemical Co., Ltd.), and examples of the amine-modified product include KF-393 (manufactured by shin-chemical Co., Ltd.).

In the flame retardant composition of the present invention, a polyol compound may be blended as a flame retardant aid as needed within a range not impairing the effects of the present invention. The polyol compound is a compound having a plurality of hydroxyl groups bonded thereto, and examples thereof include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1,3, 5-tris (2-hydroxyethyl) isocyanurate (THEIC), polyethylene glycol, glycerol, diglycerol, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose (sucrose), trehalose, inositol, fructose, maltose, and lactose. Among these polyol compounds, one or more compounds selected from the group consisting of condensates of pentaerythritol and pentaerythritol, such as pentaerythritol, dipentaerythritol, tripentaerythritol, and polypentaerythritol, are preferable, condensates of dipentaerythritol and pentaerythritol are particularly preferable, and dipentaerythritol is most preferable. Further, THEIC and sorbitol can be suitably used.

The content of the polyol compound in the flame retardant composition of the present invention is preferably 0.5 to 15 parts by mass, more preferably 2 to 12 parts by mass, and particularly preferably 5 to 10 parts by mass, based on 100 parts by mass of the total of the component (a) and the component (B).

In the flame retardant composition of the present invention, a lubricant may be blended as necessary within a range not impairing the effects of the present invention. Examples of such lubricants include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, microcrystalline paraffin, synthetic paraffin, low molecular weight polyethylene, and polyethylene wax; a halogenated hydrocarbon-based lubricant; fatty acid-based lubricants such as higher fatty acids and oxygen-containing fatty acids; fatty amide-based lubricants such as fatty amides and fatty bis-amides; ester-based lubricants such as fatty acid polyol esters (e.g., lower alcohol esters of fatty acids and glycerides), fatty acid polyglycol esters, and fatty acid alcohol esters (e.g., ester waxes); metal soaps, fatty alcohols, polyols, polyglycols, polyglycerols, partial esters of fatty acids and polyols, lubricants of partial esters of fatty acids and polyglycols, polyglycerols, silicone oils, mineral oils, and the like. The number of the lubricants may be 2 or more.

The content of the lubricant in the flame retardant composition of the present invention is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total of the components (a) and (B).

In the flame retardant composition of the present invention, one or more of a halogen-free organic or inorganic flame retardant and a flame retardant auxiliary may be used as necessary within a range not impairing the effects of the present invention. Examples of such flame retardants/flame retardant aids include triazine ring-containing compounds, metal hydroxides, phosphate ester flame retardants, condensed phosphate ester flame retardants, inorganic phosphorus flame retardants, dialkylphosphinate salts, silicone flame retardants, metal oxides, boric acid compounds, expandable graphite, other inorganic flame retardant aids, and other organic flame retardants.

Examples of the triazine ring-containing compound include melamine, ammeline, benzoguanamine, acetoguanamine, benzenedicarboxybuanamine, melamine cyanurate, butylidenebetuanamine, norbornenylbuanamine, methylenebiguanamine, ethylidene bis (melamine), trimethylene bis (melamine), tetramethylene bis (melamine), hexamethylene bis (melamine), and 1, 3-hexylidene bis (melamine).

Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and Kisuma 5A (trade name of magnesium hydroxide produced by Kyowa chemical industries Co., Ltd.).

Examples of the phosphate-based flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (dichloropropyl) phosphate, triphenyl phosphate, tricresyl phosphate, tolyldiphenyl phosphate, trixylyl phosphate, octyldiphenyl phosphate, ditolyl diphenyl phosphate, triisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tert-butylphenyl diphenyl phosphate, bis- (tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyl diphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, and the like.

Examples of the condensed phosphate-based flame retardant include 1, 3-phenylene bis (diphenyl phosphate), 1, 3-phenylene bis (dixylyl phosphate), bisphenol a bis (diphenyl phosphate), and the like.

The inorganic phosphorus flame retardant may be red phosphorus.

Examples of the dialkylphosphinic salts include aluminum diethylphosphinate and zinc diethylphosphinate.

Examples of the other inorganic flame retardant aid include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and hydrotalcite, and surface-treated products thereof. As specific examples thereof, various commercially available products such as TIPAQUE R-680 (trade mark of titanium oxide produced by Shigaku corporation), Kyowamag 150 (trade mark of magnesium oxide produced by Kyowa Kagaku corporation), DHT-4A (hydrotalcite: manufactured by Kyowa Kagaku corporation), Alcamizer 4 (trade mark of zinc-modified hydrotalcite manufactured by Kyowa Kagaku corporation) and the like can be used.

The flame retardant composition of the present invention may contain, as necessary, a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, an ultraviolet absorber, a hindered amine compound other than the component (B), an antioxidant, and the like. These components may be previously blended in the flame retardant composition of the present invention, or may be blended in a synthetic resin when blended in the synthetic resin. The synthetic resin is stabilized by compounding these components.

Examples of the phenol-based antioxidant include 2, 6-di-t-butyl-p-cresol, 2, 6-diphenyl-4-octadecyloxyphenol, distearyl (3, 5-di-t-butyl-4-hydroxybenzyl) phosphonate, 1, 6-hexamethylenebis [ (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide ], 4 ' -thiobis (6-t-butyl-m-cresol), 2 ' -methylenebis (4-methyl-6-t-butylphenol), 2 ' -methylenebis (4-ethyl-6-t-butylphenol), 4 ' -butylidenebis (6-t-butyl-m-cresol), 2 ' -ethylenebis (4, 6-di-tert-butylphenol), 2' -ethylenebis (4-sec-butyl-6-tert-butylphenol), 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) -2,4, 6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 2-tert-butylidenebis (4-methyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, Octadecyl (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] methane, thiodiethylene glycol bis [ (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 1, 6-hexamethylenebis [ (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], bis [3, 3-bis (4-hydroxy-3-t-butylphenyl) butyrate ] diol bis [ 2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-methylbenzyl) phenyl ] terephthalate, 1,3, 5-tris [ (3, 5-di-t-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 ], and the like.

The amount of the phenol antioxidant to be used is preferably 0.001 to 5% by mass, more preferably 0.05 to 3% by mass, in the resin composition when the phenol antioxidant is blended in the synthetic resin.

Examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite, tris [ 2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylsulfanyl) -5-methylphenyl ] phosphite, tridecyl phosphite, octyldiphenyl phosphite, didecylmonophenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, 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-diisopropylphenyl) pentaerythritol diphosphite, tris [2, 4-diisopropylphenyl ] pentaerythritol diphosphite, tris [ 2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylsulfanyl) -5-methylphenyl ] phosphite, Tetrakis (tridecyl) isopropylidenediphenol diphosphite, tetrakis (tridecyl) -4,4 ' -n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2, 4-di-tert-butylphenyl) biphenylene diphosphonite, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2 ' -methylenebis (4, 6-tert-butylphenyl) -2-ethylhexyl phosphite, 2 ' -methylenebis (4, 6-tert-butylphenyl) -octadecyl phosphite, tetra (tridecyl) -4,4 ' -n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, 2, 4-di-tert-butylphenyl) butanetriphosphite, tetrakis (2, 4-di-tert-butylphenyl) biphenylene diphosphonite, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2 ' -methylenebis (4, 6-tert-butylphenyl) -2-ethylhexyl phosphite, 2, 2' -ethylidenebis (4, 6-di-tert-butylphenyl) fluorophosphite, tris (2- [ (2,4,8, 10-tetra-tert-butyldibenzo [ d, f ] -1, 3, 2] dioxaphosphepin-6-yl) oxy ] ethyl) amine, 2-ethyl-2-butylpropanediol phosphite and 2,4, 6-tri-tert-butylphenol, and the like.

When the phosphorus-based antioxidant is blended in the synthetic resin, the amount of the phosphorus-based antioxidant to be used is preferably 0.001 to 5% by mass, and more preferably 0.05 to 3% by mass in the resin composition.

Examples of the thioether-based antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate, and pentaerythritol tetrakis (. beta. -alkylmercaptopropionate).

The amount of the thioether antioxidant to be used is preferably 0.001 to 5% by mass, more preferably 0.05 to 3% by mass, in the resin composition when the thioether antioxidant is blended in the synthetic resin.

Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, and 5, 5' -methylenebis (2-hydroxy-4-methoxybenzophenone); 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 '-hydroxyphenyl) benzotriazoles such as 2- (2' -hydroxy-3 ', 5' -dicumylphenyl) benzotriazole, 2 '-methylenebis (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 oxalanilides such as 2-ethyl-2 '-ethoxyoxalanilide and 2-ethoxy-4' -dodecyloxalanilide; cyanoacrylates such as ethyl- α -cyano- β, β -diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; triaryltriazines such as 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, and 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4, 6-bis (2, 4-di-tert-butylphenyl) -s-triazine.

When the ultraviolet absorber is blended in the synthetic resin, the amount of the ultraviolet absorber is preferably 0.001 to 5% by mass, and more preferably 0.05 to 3% by mass in the resin composition.

Examples of the other hindered amine compound 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-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3, 4-butane tetracarboxylic acid ester, tetrakis (1,2,2,6, 6-pentamethyl-4-piperidinyl) -1,2,3, 4-butanetetracarboxylate, bis (2,2,6, 6-tetramethyl-4-piperidinyl) bis (tridecyl) -1,2,3, 4-butanetetracarboxylate, 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-piperidylamino) hexane/2, 4-dichloro-6-morpholinyl-s-triazine polycondensate, 1, 6-bis (2,2,6, 6-tetramethyl-4-piperidylamino) hexane/2, 4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8, 12-tetrakis [2, 4-bis (N-butyl-N- (2,2,6, 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl ] -1,5,8, 12-tetraazadodecane, 1,5,8, 12-tetrakis [2, 4-bis (N-butyl-N- (1, hindered amine compounds such as 2,2,6, 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl ] -1,5,8, 12-tetraazadodecane, 1,6, 11-tris [2, 4-bis (N-butyl-N- (2,2,6, 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl ] aminoundecane, and 1,6, 11-tris [2, 4-bis (N-butyl-N- (1,2,2,6, 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl ] aminoundecane.

The amount of the other hindered amine compound to be used is preferably 0.001 to 5% by mass, and more preferably 0.05 to 3% by mass in the resin composition when the compound is blended in a synthetic resin.

Examples of the antioxidant include naphthylamine type, diphenylamine type, p-phenylenediamine type, quinoline type, hydroquinone derivative, monophenol type, thiobisphenol type, hindered phenol type, phosphite type and the like.

The amount of the antioxidant to be used is preferably 0.001 to 5% by mass, more preferably 0.05 to 3% by mass, in the resin composition when the antioxidant is blended in the synthetic resin.

The flame retardant composition of the present invention may contain a reinforcing material as an optional component within a range not impairing the effects of the present invention. These ingredients may be compounded in the synthetic resin when the flame retardant composition of the present invention is compounded in the synthetic resin. As the reinforcing material, those in a fiber form, a plate form, a granular form, or a powder form, which are generally used for reinforcing synthetic resins, 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 whiskers, silicon whiskers, wollastonite, sepiolite, asbestos, slag fibers, xonotlite, wollastonite, gypsum 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, kapok, jute, hemp, agaropetalum, flax, linen, silk, manila hemp, sugarcane, wood pulp, paper dust, used paper, and wool, glass flakes, nonswelling mica, graphite, metal foils, ceramic beads, clay, mica, sericite, graphite, and the like, A plate-like or granular reinforcing material such as zeolite, bentonite, dolomite, kaolin, finely powdered silicic acid, feldspar powder, potassium titanate, white sand balls (shirasu balloon), calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, dense quartzite (novaculite), dawsonite (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 an aminosilane or an epoxy silane.

The flame retardant composition of the present invention may further contain a crystal nucleating agent as an optional component within a range not impairing the effects of the present invention. As the crystal nucleus agent, those generally used as polymer crystal nucleus agents can be suitably used, and in the present invention, either of inorganic crystal nucleus agents and organic crystal nucleus agents can be used. These ingredients may be compounded in the synthetic resin when the flame retardant composition of the present invention is compounded in the synthetic resin.

Specific examples of the inorganic crystal nucleating agent include metal salts such as 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 phenylphosphonate. These inorganic crystal nucleating agents can be modified with organic substances to improve dispersibility in the composition.

Specific examples of the organic crystal nucleating agent include organic carboxylic acid metal salts 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 -naphthalenedicarboxylate, sodium cyclohexanecarboxylate, and 4-tert-butylbenzoate, organic sulfonic acid salts such as sodium p-toluenesulfonate, sodium sulfoisophthalate, and the like, And carboxylic acid amides such as stearamide, ethylenebislauramide, palmitamide, hydroxystearamide, erucamide and tri (t-butylamide) trimesic acid, benzylidene sorbitol and its derivatives, phosphorus compound metal salts such as sodium-2, 2' -methylenebis (4, 6-di-t-butylphenyl) phosphate, and sodium 2, 2-methylbis (4, 6-di-t-butylphenyl) salt.

In the flame retardant composition of the present invention, an acrylic processing aid may be further added as an optional component within a range not impairing the effects of the present invention. The acrylic processing aid may be obtained by polymerizing 1 kind of (meth) acrylic acid ester or copolymerizing 2 or more kinds of (meth) acrylic acid ester. These ingredients may be compounded in the synthetic resin when the flame retardant composition of the present invention is compounded in the synthetic resin. Examples of the (meth) acrylate to be polymerized or 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. In addition to these, there may be mentioned (meth) acrylic acid and hydroxyl group-containing (meth) acrylates.

The flame retardant composition of the present invention may contain a plasticizer as an optional component within a range not impairing the effects of the present invention. As such a plasticizer, those generally used as plasticizers for polymers can be suitably used, and examples thereof include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, epoxy plasticizers, and the like.

These ingredients may be compounded in the synthetic resin when the flame retardant composition of the present invention is compounded in the synthetic resin.

In the flame retardant composition of the present invention, additives usually used in synthetic resins, for example, crosslinking agents, antistatic agents, metal soaps, fillers, antifogging agents, anti-deposition and scale-forming agents, surface treatment agents, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, mold release agents, pigments, neutralizing agents, processing aids other than acrylic processing aids, and the like may be blended as necessary within a range not impairing the effects of the present invention.

These ingredients may be compounded in the synthetic resin when the flame retardant composition of the present invention is compounded in the synthetic resin.

The flame retardant composition of the present invention can be obtained by mixing the component (a) and the component (B), and further optionally other components as required, and various mixers can be used for mixing. Heating may be performed during mixing. Examples of usable mixers include a tumbler mixer, a henschel mixer, a ribbon mixer, a V-type mixer, a W-type mixer, a super mixer, and a nauta mixer.

The flame retardant composition of the present invention is effective for making synthetic resins flame retardant, and can be preferably used as a flame-retardant synthetic resin composition by being blended with synthetic resins.

Specific examples of the synthetic resin flame-retarded by the flame retardant composition of the present invention include polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, crosslinked polyethylene, ultrahigh molecular weight polyethylene, poly-1-butene, alpha-olefin polymers such as poly-3-methylpentene, ethylene-vinyl acetate copolymers, polyolefins such as ethylene-ethyl acrylate copolymers and ethylene-propylene copolymers, and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, polyethylene-vinyl chloride copolymers, polyethylene-vinyl acetate copolymers, polyethylene-vinyl chloride copolymers, polyethylene-vinyl acetate copolymers, polyethylene-vinyl chloride copolymers, polyethylene-vinyl acetate copolymers, polyethylene-vinyl chloride copolymers, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene, Halogen-containing resins such as vinyl chloride-acrylate copolymers, vinyl chloride-maleate copolymers, and vinyl chloride-cyclohexylmaleimide copolymers; petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; aromatic polyesters such as polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, and polycyclohexanedimethylene terephthalate, polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate, and linear polyesters such as polytetramethylene terephthalate; degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid resin, polymalic acid, polydiol acid, polydioxan, and poly (2-oxetanone); thermoplastic resins such as polyphenylene oxide, polyamide and polyhexamethylene adipamide, polycarbonate, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane and cellulose resins, blends thereof, thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins and unsaturated polyester resins, fluorine resins, silicone resins, polyether sulfones, polysulfones, polyphenylene ethers, polyether ketones, polyether ether ketones and liquid crystal polymers. Further, isoprene rubber, butadiene rubber, propylene-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, and the like can be cited.

Further, other specific examples of the synthetic resin to be flame-retardant 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, polyamide-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and the like.

These synthetic resins may be used in 1 kind or 2 or more kinds. Also, the synthetic resin may be alloyed.

The synthetic resin used in the present invention can be used regardless of the molecular weight, polymerization degree, density, softening point, proportion of insoluble matter in a solvent, degree of stereoregularity, presence or absence of catalyst residue, kind of monomer to be a raw material, compounding ratio, kind of polymerization catalyst (for example, ziegler-type catalyst, metallocene catalyst, etc.), and the like.

Among these synthetic resins, polyolefin resins are preferred in terms of imparting excellent flame retardancy.

Examples of the polyolefin-based resin include polyethylene, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, homopolypropylene, random copolymer polypropylene, block copolymer polypropylene, impact copolymer polypropylene, high-impact copolymer polypropylene, isotactic polypropylene, syndiotactic polypropylene, and alpha-olefin polymers such as hemi-isotactic polypropylene, maleic anhydride-modified polypropylene, polybutene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, and the like, and alpha-olefin copolymers such as ethylene/propylene block or random copolymers, ethylene/methyl methacrylate copolymers, ethylene/vinyl acetate copolymers, and the like.

The total content of the component (a) and the component (B) in the flame-retardant synthetic resin composition of the present invention is preferably 10 mass% or more and less than 60 mass%, more preferably 20 mass% or more and less than 50 mass%, and particularly preferably 25 mass% or more and less than 45 mass%, from the viewpoint of flame retardancy. If the amount is less than 10% by mass, sufficient flame retardancy may not be exhibited, and if the amount is 60% by mass or more, the original physical properties of the resin may be deteriorated.

The flame-retardant resin composition of the present invention can be molded to obtain a molded article having excellent flame retardancy. The molding method is not particularly limited, and examples thereof include extrusion, calendering, injection molding, roll molding, compression molding, blow molding, and the like, and molded articles having various shapes such as resin plates, sheets, films, and profiles can be produced.

The flame-retardant resin composition of the present invention can be used for housings (frames, housings, covers, and exterior parts) of electric vehicles, machines, electric/electronic devices, OA devices, and the like, parts, automotive interior and exterior materials, and can be suitably used for applications requiring the specification of UL-94 VTM.

The flame-retardant synthetic resin composition and the molded article thereof of the present invention can be used in a wide range of industrial fields such as electric, electronic and telecommunication, agriculture, forestry, marine industry, mining industry, construction, food, fiber, clothing, medical treatment, stone charcoal, petroleum, rubber, leather, automobile, precision equipment, wood, building materials, civil engineering, furniture, printing, musical instruments, and the like. More specifically, the present invention can be used in a case (frame, case, cover, etc.) of a printer, a personal computer, a word processor, a keyboard, a PDA (small information terminal), a telephone, a copier, a facsimile machine, an ECR (electronic cash register), an electronic calculator, an electronic account, a card, a cradle, a business such as stationery, an OA equipment, a washing machine, a refrigerator, a cleaner, a microwave oven, a lighting equipment, a game machine, an electric iron, a home appliance such as a heating oven, an AV equipment such as a TV, a VTR, a video camera, a recorder (boombox), a recorder, a compact disc, a CD player, a speaker, a liquid crystal display, a connector, a relay, a capacitor, a switch, a printed circuit board, a bobbin, a semiconductor sealing material, an LED sealing material, a wire, a cable, a transformer, a deflection coil, an electric/electronic part such as a switchboard, a clock, a communication equipment, OA equipment, etc Exterior trim), parts, automotive interior and exterior trim materials.

The flame-retardant synthetic resin composition and the molded article thereof of the present invention can be used for seats (fillers, upholstery fabrics, etc.), seat belts, ceiling coverings, ceilings, armrests, door trims, rear luggage trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulating materials, pull rings, wire covering materials, electric insulating materials, paints, coating materials, covering materials, floor materials, corner walls, carpets, wallpaper, wall coverings, exterior materials, interior materials, roof materials, deck materials, wall materials, column materials, underlay sheets, enclosure materials, frames and moldings, window and door-shaped materials, shingles, sidings, terraces, balconies, sound-insulating sheets, heat-insulating sheets, window materials, etc., automobiles, hybrid vehicles, electric vehicles, ships, airplanes, buildings, houses and building materials, civil engineering materials, building materials, wall coverings, balcony, sound-insulating sheets, window materials, etc, Clothing, curtains, bed sheets, plywood, synthetic fiber boards, carpets, door buckle mats, seat cushions, buckets, pipes, containers, glasses, leather bags, boxes, goggles, skis, rackets, tents, musical instruments and other living goods, sports goods and other various uses.

Examples

The present invention will be described in detail below with reference to examples. However, the present invention is not limited in any way by the following examples. The blending amounts in the following tables are based on parts by mass.

Examples 1 to 6 and comparative examples 1 to 9

Resin compositions (examples 1 to 6) containing the flame retardant composition of the present invention and comparative resin compositions (comparative examples 1 to 9) were prepared by blending various components in the formulations shown in tables 1 and 2.

(A) The phosphate flame retardant of component (A) was prepared by mixing component (A-1) and component (A-2) in the following manner, wherein the ratio of component (A-1) to component (A-2) was adjusted to 30: 70. 35: 65. 40: 60 and 45: 55 by mass ratio.

Production example 1

(A-1) component: melamine salts

Melamine orthophosphate was subjected to a condensation reaction under heating at 220 ℃ in a solid phase state for 6 hours to produce a melamine salt containing melamine pyrophosphate as a main component. The melamine salt was used without purification. The purity of melamine pyrophosphate in the melamine salt was 98.5%.

The purity was analyzed using a Thermo Fisher Scientific K.K. system Ion chromatograph (ICS-2100), a Thermo Fisher Scientific K.K. system column (Dionex Ion Pac AS-19), a conductivity detector, and an aqueous potassium hydroxide solution (eluent).

Production example 2

(A-2) component: piperazine salts

Piperazine orthophosphate was subjected to a condensation reaction at 250 ℃ in a solid phase for 1 hour to produce a piperazine salt containing piperazine pyrophosphate as a main component. The piperazine salt was used as it was without purification. The purity of piperazine pyrophosphate in the piperazine salt was 99.0%.

The purity was analyzed using a Thermo Fisher Scientific K.K. system Ion chromatograph (ICS-2100), a Thermo Fisher Scientific K.K. system column (Dionex Ion Pac AS-19), a conductivity detector, and an aqueous potassium hydroxide solution (eluent).

(B) Component (b) hindered amine compound the following hindered amine compounds 1 and 2 were used as the compound having the structure represented by chemical formula (1).

Hindered amine compound 1: ADK STAB LA-63P (manufactured by ADEKA, Inc., general formula (2))¹Is CH₃A compound of (1)

Hindered amine compound 2: ADK STAB LA-68 (manufactured by ADEKA, Inc., general formula (2))¹A compound of formula H)

In the comparative examples, the following hindered amine compounds 3 to 5 having no structure represented by the chemical formula (1) were used for comparison with the hindered amine compound of the component (B) used in the examples.

Hindered amine compound 3:

hindered amine compound 4:

hindered amine compound 5:

the flame-retardant synthetic resin compositions obtained were extruded at 200 ℃ to produce pellets, in which the components described in tables 1 and 2 were compounded. The obtained pellets are press-molded at 200 ℃ to obtain a film sample for a flame retardancy test having a thickness of 0.37 to 0.47 mm. Using the film sample, the UL-94VTM test was carried out by the test method described below. The results are shown in tables 1 and 2.

< UL-94VTM flame retardancy test method >

Each film sample was evaluated according to the UL-94VTM method. The sample was cut into 20 cm. times.5 cm and placed at 23. + -. 2 ℃ and 50. + -. 5% RH for 48 hours. Then, the sample was wound into a cylindrical shape so that the lower ends thereof did not overlap, and the lower end of the sample was vertically held above the burner by 10 mm. The lower end of the sample was brought into contact with the flame for 3 seconds using a bunsen burner having an inner diameter of 9.5mm and a flame length of 20mm as a heat source, and then the number of seconds of combustion was measured. After extinguishing, the flame was again exposed for 3 seconds, and the number of seconds of combustion was measured. Flame retardancy was evaluated according to the evaluation standards of VTM-0, VTM-1, and VTM-2, and the rating of the test piece corresponding to the lowest standard among the number of measurements with n equal to 5 was taken as the evaluation rating of the resin composition. Any one of the levels not corresponding to VTM-0 to VTM-2 is defined as NR (No rating). The cotton placed under the test piece was also evaluated for ignition due to the falling seeds of fire, and the number of times of ignition was recorded.

[ Table 1]

*1: low-density polyethylene (manufactured by Japan Polypropylene Corporation: Novatec LF441B)

*2: tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl ] methane (manufactured by ADEKA: ADK STAB AO-60)

*3: tris (2, 4-di-tert-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Co., Ltd.)

*4: calcium stearate

*5: glycerol monostearate

[ Table 2]

Examples 7 to 9 and comparative examples 10 to 16

Resin compositions (examples 7 to 9) containing the flame retardant composition of the present invention and comparative resin compositions (comparative examples 10 to 16) were prepared by blending various components in the formulations shown in tables 3 and 4. The obtained flame-retardant synthetic resin composition was subjected to UL-94VTM test in the same manner as in example 1. The results are shown in tables 3 and 4.

(A) As the phosphate flame retardant of component (A), a melamine polyphosphate salt as component (A-1) produced in the same manner as in production example 1 and a piperazine polyphosphate salt as component (A-2) produced in the same manner as in production example 2 were used.

[ Table 3]

[ Table 4]

As shown in tables 1 to 4, in the results of the UL-94VTM flame retardancy test, the results of VTM-2 were evaluated in examples 1 to 9, while those of comparative examples 1 to 16 were evaluated for NR.