JP4721823B2 - Flame retardant resin composition and molded body comprising the same - Google Patents

Description

  The present invention relates to a flame retardant resin composition and a molded body comprising the same.

Polyolefin resins are widely used in building materials, automobile parts, packaging materials, agricultural materials, housing materials for home appliances, toys, etc. due to their excellent chemical and mechanical properties. However, polyolefin resin is a flammable substance, and flame retardant is indispensable depending on applications.
As a flame retardant method, it is widely known to use a halogen flame retardant, a phosphorus flame retardant, a metal hydroxide or a nitrogen compound alone or in combination.

  In recent years, there has been a demand for a non-halogen flame retardant polyolefin resin composition having excellent flame retardancy without using a halogen flame retardant that generates a toxic gas during combustion.

  For example, for applications of molded products such as films, sheets, pipes, containers, electric wires, and cables, a crosslinkable flame retardant composition in which a flame retardant and red phosphorus are blended with a polyolefin resin is disclosed (Patent Document 1). reference). In this document, additive-type flame retardants such as phosphorus flame retardants and inorganic flame retardants are listed as flame retardants.

  However, any of the resin materials using these flame retardants contains a very high concentration of flame retardant, so there is no problem when used for thick sheets and various molded products. When it is used for the above, only fibers and films having low physical properties can be obtained. In addition, production stability during yarn production or film formation is also a problem. Furthermore, in the case of thin molded articles such as fibers and films, when the thickness or diameter is less than 0.3 mm, there is a problem that flame retardancy is remarkably reduced.

As a technique for thin flame-retardant fibers, there is an example in which a phosphoric ester amide is blended with a thermoplastic resin, particularly an engineering plastic (see Patent Document 2). In that example, 10 parts by weight or more of phosphoric ester amide is blended with 100 parts by weight of engineering plastics such as polyethylene terephthalate and polyamide to produce flame retardant fibers.
However, when 10 parts by weight or more of phosphoric ester amide is blended with polyolefin, phosphoric ester amide is significantly bleeded out during kneading and molding, so that kneading and molding are impossible. On the other hand, even when phosphoric ester amide is added to polyolefin in the amount of about 1% by mass of the usual additive, flame retardancy is not sufficiently exhibited.

  By the way, among hindered amine compounds known as light-resistant stabilizers, it is disclosed that, in particular, the NOR type hindered amine compound exhibits flame retardancy performance at the additive blending amount in the region of the thickness of thin molded articles such as fibers and films. (See Patent Document 3). This NOR-type hindered amine compound can be added to various resin materials, and since the blending amount is about the same as an additive, there is no problem in the stability during yarn production and film formation. However, the flame retardancy is not always sufficient.

Further, in order to improve flame retardancy, a combined use (about the amount of additive) of a NOR-type hindered amine compound and a phosphate ester flame retardant has been proposed (see Patent Document 4). However, the flame retardancy was not sufficient.
JP-A-7-102128 JP 2004-59843 A International Publication No. 99/00450 Brochure JP 2001-348724 A

  The present invention has been made in view of the above-described problems, and provides a flame-retardant resin composition that can provide a molded product having high flame retardancy, even a fiber or a thin molded article, and a molded article comprising the same. With the goal.

  The inventors of the present invention have intensively studied to solve the above-mentioned problems. As a result, by adding a small amount of a phosphoric ester amide flame retardant to a flame retardant resin composition comprising a polyolefin / NOR type hindered amine compound, It has been found that the flame retardancy of thin molded articles can be improved. Moreover, it discovered that a flame retardance could be improved further by adding an inorganic flame retardant to this flame retardant resin composition, and completed this invention.

[式中、Ｒ^１〜Ｒ^４はそれぞれ水素原子又は下記式（２）の有機基を表す。Ｒ^１〜Ｒ^４の少なくとも１つは下記式（２）の有機基である。

（式中、Ｒ^５は炭素数１〜１７のアルキル基、炭素数５〜１０のシクロアルキル基、フェニル基又は炭素数７〜１５のフェニルアルキル基を表し、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９はそれぞれ炭素数１〜４からなるアルキル基を表す。Ｒ^１０は水素原子、又は炭素数１〜１２の直鎖あるいは分岐鎖のアルキル基を表す。）] According to the present invention, the following flame retardant resin composition and molded article are provided.
1. A flame retardant resin composition comprising the following components (A) to (C).
(A) Polyolefin resin: 90-99.6% by mass
(B) Phosphate ester amide: 0.2 to 8% by mass
(C) NOR type hindered amine stabilizer represented by the following formula (1): 0.2 to 2% by mass

[Wherein, R ^{1 to} R ⁴ each represents a hydrogen atom or an organic group of the following formula (2). At least one of R ^{1 to} R ⁴ is an organic group of the following formula (2).

(In the formula, R ⁵ represents an alkyl group having 1 to 17 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a phenyl group, or a phenylalkyl group having 7 to 15 carbon atoms, and R ⁶ , R ⁷ , R ⁸ and R ⁹ represents an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms.

2. Furthermore, the flame-retardant resin composition of 1 which contains 0.2-5 mass% of (D) inorganic flame retardant with respect to the total amount of said component (A)-(D).

［式中、Ａ^１〜Ａ^４は、それぞれ−ＯＲ^１１（Ｒ^１１はアルキル基、シクロアルキル基又はアリール基を示し、これらの基は置換基を有していてもよい）又は−ＮＲ^１２Ｒ^１３（Ｒ^１２及びＲ^１３は、それぞれ水素原子、アルキル基、シクロアルキル基又はアリール基を示す。これらは置換基を有していてもよく、また、Ｒ^１２及びＲ^１３は互いに結合して環を形成していてもよい。）を示す。Ａ^５はジアミン残基又はアリーレンジオキシ基を示し、ｎは０〜２０の整数を示す。Ａ^５がジアミン残基でない場合、Ａ^１〜Ａ^４の少なくとも１つは、−ＮＲ^１２Ｒ^１３で示される基である。］ 3. The flame retardant resin composition according to 1 or 2, wherein the phosphoric ester amide of the component (B) is a compound represented by the following formula (3).

[Wherein, A ^{1 to} A ⁴ each represent —OR ¹¹ (R ¹¹ represents an alkyl group, a cycloalkyl group, or an aryl group, and these groups optionally have a substituent) or —NR ¹² R ¹³ (R ¹² and R ¹³ each represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. These may have a substituent, and R ¹² and R ¹³ are bonded to each other to form a ring. May be formed). A ⁵ represents a diamine residue or an arylenedioxy group, and n represents an integer of 0 to 20. If A ⁵ is not a diamine ^residue, at least one of A 1 to A ^{4 is} a group represented by ^-NR 12 ^{R 13.} ]

（式中、Ｒ^１４及びＲ^１５は、それぞれ水素原子、アルキル基、又はシクロアルキル基を示し、Ｒ^１４及びＲ^１５は互いに結合して環を形成してもよい。Ｚ^１はアルキレン基、シクロアルキレン基又は二価の芳香族性基を示す。Ｚ^２は二価の芳香族性基を示す。） 4). The flame-retardant resin composition according to 3, wherein A ^{5 in the} formula (3) is an organic group represented by the following formula (4) or (5).

(Wherein R ¹⁴ and R ¹⁵ each represent a hydrogen atom, an alkyl group, or a cycloalkyl group, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Z ¹ represents an alkylene group, An alkylene group or a divalent aromatic group; Z ² represents a divalent aromatic group.)

5. The inorganic flame retardant of component (D) is at least one flame retardant selected from hydrotalcite, dolomite compounds, magnesium oxide, zinc borate and zinc stannate, The flame-retardant resin composition as described.
6). A thin molded article having a thickness of less than 0.3 mm, comprising the flame retardant resin composition according to any one of 1 to 5 above.
7). The fiber which consists of a flame-retardant resin composition in any one of said 1-5.

  In the flame-retardant resin composition of the present invention, a molded product having high flame retardancy can be obtained even if it is a fiber or a thin molded product having a thickness of less than 0.3 mm.

Hereinafter, the flame retardant resin composition of the present invention will be specifically described.
The flame retardant resin composition of the present invention includes the following components (A) to (C).
(A) Polyolefin resin: 90-99.6% by mass
(B) Phosphate ester amide: 0.2 to 8% by mass
(C) NOR type hindered amine stabilizer represented by the formula (1) described later: 0.2 to 2.0% by mass
In addition, a mass fraction means the value with respect to the total mass of said (A)-(C) component.
Furthermore, it is preferable to contain 0.2-5 mass% of (D) inorganic flame retardant with respect to the total amount of component (A)-(D). In addition, what is necessary is just to reduce the mixing ratio of a component (A) by the part which added the component (D) to the composition. That is, the mixing ratio of the polyolefin resin as the component (A) is 85 to 99.4% by mass.
Hereinafter, components (A) to (D) will be described.

(A) Polyolefin resin Examples of the polyolefin resin include a polypropylene resin, a polyethylene resin, and an olefin synthetic rubber.

  Examples of the polypropylene resin include a propylene homopolymer (polypropylene) and a copolymer mainly composed of propylene. Examples of the copolymer include a propylene / α-olefin copolymer. Examples of the α-olefin include ethylene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-butene. , 1-pentene and the like.

  Examples of the polyethylene resin include low density polyethylene, medium density polyethylene, and high density polyethylene.

  Examples of the olefin-based synthetic rubber include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-1-butene rubber, and ethylene-vinyl acetate rubber.

Among these, a propylene homopolymer and a low density polyethylene that are excellent in the stretching effect are preferable.
The higher the melt index (MI) of the polyolefin resin, the higher the flame retardancy.
Specifically, a polyolefin resin having an MI measured under conditions of a temperature of 230 ° C. and a load of 2.16 kg / 10 minutes is preferably 3 (g / 10 minutes) or more, and particularly MI is 10 (g / 10 minutes) or more. A certain polyolefin resin is preferable from the viewpoint of flame retardancy. However, if MI exceeds 30 (g / 10 minutes), it is difficult to form a film. If MI exceeds 50 (g / 10 minutes), fibers can be formed. I can't get it.

The blending amount of the component (A) in the total mass of the components (A) to (C) is 90 to 99.6% by mass, preferably from the relationship with the blending amount of the components (B) to (C) described later. It is 96.2-99.4 mass%, Most preferably, it is 96.7-99.0 mass%.
Moreover, the compounding quantity of (A) component which occupies the total mass of component (A)-(D) when compounding component (D) is 85-99.4 mass%, Preferably it is 94.2-99. The content is 1% by mass, particularly preferably 94.9 to 98.5% by mass.

［式中、Ａ^１〜Ａ^４は、それぞれ−ＯＲ^１１（Ｒ^１１はアルキル基、シクロアルキル基又はアリール基を示し、これらの基は置換基を有していてもよい）又は−ＮＲ^１２Ｒ^１３（Ｒ^１２及びＲ^１３は、それぞれ水素原子、アルキル基、シクロアルキル基又はアリール基を示す。これらは置換基を有していてもよく、また、Ｒ^１２及びＲ^１３は互いに結合して環を形成していてもよい。）を示す。Ａ^５はジアミン残基又はアリーレンジオキシ基を示し、ｎは０〜２０の整数を示す。Ａ^５がジアミン残基でない場合、Ａ^１〜Ａ^４の少なくとも１つは、−ＮＲ^１２Ｒ^１３で示される基である。］ (B) Phosphoric ester amide The phosphoric ester amide may be a compound having a bond of phosphoric ester and phosphoric amide.
For example, a compound represented by the following formula (3) is preferable.

[Wherein, A ^{1 to} A ⁴ each represent —OR ¹¹ (R ¹¹ represents an alkyl group, a cycloalkyl group, or an aryl group, and these groups optionally have a substituent) or —NR ¹² R ¹³ (R ¹² and R ¹³ each represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. These may have a substituent, and R ¹² and R ¹³ are bonded to each other to form a ring. May be formed). A ⁵ represents a diamine residue or an arylenedioxy group, and n represents an integer of 0 to 20. If A ⁵ is not a diamine ^residue, at least one of A 1 to A ^{4 is} a group represented by ^-NR 12 ^{R 13.} ]

In formula (3), examples of the alkyl group represented by R ¹¹ , R ¹² and R ¹³ include C _1-20 such as methyl, ethyl, propyl, butyl, t-butyl, pentyl, hexyl, octyl, nonyl and dodecyl. An alkyl group, preferably a C _1-12 alkyl group, more preferably a C _1-6 alkyl group can be mentioned.
Examples of the cycloalkyl group include C _5-20 cycloalkyl groups such as cyclopentyl and cyclohexyl, preferably C _6-12 cycloalkyl groups.
_{Examples of the} aryl group include C _6-20 aryl groups such as phenyl and naphthyl, and substituted aryl groups (methylphenyl group, ethylphenyl group, hydroxyphenyl group, etc.).
R ¹² and R ¹³ may be bonded to each other to form a ring (for example, a 4- to 10-membered heterocycle having an adjacent nitrogen atom as a hetero atom). These groups may have a substituent (for example, a C _1-4 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, etc., particularly a C _1-3 alkyl group; a hydroxyl group, etc.).

As the —OR ¹¹ group, a monovalent organic group such as phenyloxy, tolyloxy, xylyloxy, trimethylphenyloxy, ethylphenyloxy, methylethylphenyloxy, diethylphenyloxy, triethylphenyloxy, propylphenyloxy, isopropylphenyloxy And phenyloxy group optionally having a substituent (C _1-3 alkyl group and the like) such as diisopropylphenyloxy and hydroxyphenyloxy.

As the —NR ¹² R ¹³ group, a monovalent amino group, for example, a mono- or di-C ₁ -C ₄ alkylamino group such as methylamino, butylamino, dimethylamino, dibutylamino; mono- or di-C ₄ such as cyclohexylamino; -C ₁₂ cycloalkyl-substituted amino group; _C 1 -C ₄ alkyl _C 6 methyl phenylamino, etc. _{- 20} arylamino group; phenylamino, mono- or _di-C 6 _{-C 20} arylamino groups such as diphenylamino pyrrolidino, 2 A 4- to 10-membered (preferably 5- to 8-membered) heterocycle having at least one nitrogen atom as a hetero atom, such as methylpyrrolidino, piperidino, 2-methylpiperidino (pipecolino), 3-methylpiperidino, 4-methylpiperidino, piperazino Groups and the like.

Further, A ¹ and A ² adjacent to each other, and A ³ and A ⁴ may be bonded to each other to form a ring. For example, an alkylenedioxy group (for example, methylenedioxy, dimethylenedioxy, trimethylenedioxy, 2,2-dimethyl-1,3-trimethylenedioxy, 2-ethyl-2-methyl-1,3-trimethyl) methylenedioxy, _{2,2-diethyl-1,3-C} 2 _{-C 10} alkylenedioxy trimethylenedioxy, etc.) and the like may be formed.

（式中、Ｒ^１４及びＲ^１５は、それぞれ水素原子、アルキル基、又はシクロアルキル基を示し、Ｒ^１４及びＲ^１５は互いに結合して環を形成してもよい。Ｚ^１はアルキレン基、シクロアルキレン基又は二価の芳香族性基を示す。Ｚ^２は二価の芳香族性基を示す。） In the formula (3), A ⁵ may be a divalent group represented by the following formula (4) or (5).

(Wherein R ¹⁴ and R ¹⁵ each represent a hydrogen atom, an alkyl group, or a cycloalkyl group, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Z ¹ represents an alkylene group, An alkylene group or a divalent aromatic group; Z ² represents a divalent aromatic group.)

Examples of the alkyl group and cycloalkyl group represented by R ¹⁴ and R ¹⁵ include the above-exemplified alkyl groups (C _1-6 alkyl groups such as methyl and ethyl) and cycloalkyl groups (C _4-10 cyclo such as cyclohexyl). Alkyl group, etc.). R ¹⁴ and R ¹⁵ may be bonded to each other to form a C _1-6 alkylene group such as methylene, ethylene, propylene, tetramethylene or hexamethylene.

Examples of the alkylene group represented by Z ¹ include C _1-6 alkylene groups such as methylene, ethylene, propylene, tetramethylene, hexamethylene, and preferably C _1-4 alkylene groups. Examples thereof include C _4-20 cycloalkylene groups such as _silene , preferably C _6-12 cycloalkylene groups.
Examples of the divalent aromatic group represented by Z ¹ and Z ² include an arylene group (for example, a C _6-20 arylene group such as phenylene and naphthylene groups), a group having a plurality of the arylene groups [for example, Bisphenols (dihydroxydiarylalkanes such as bisphenol A, bisphenol D, bisphenol AD, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane; Dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane; dihydroxyarylalkylbenzenes such as 1,4-bis (4-hydroxyphenylisopropyl) benzene; bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxy Dihydroxydiaryl sulfones such as phenyl) sulfone; dihydroxydiaryl ethers such as bis (4-hydroxyphenyl) ether and bis (3,5-dimethyl-4-hydroxyphenyl) ether; 4,4′-dihydroxybenzophenone, 3, Dihydroxy diaryl ketones such as 3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone; dihydroxys such as bis (4-hydroxyphenyl) sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide Diaryl sulfides; dihydroxy diaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide; dihydroxy diphenyls such as 4,4′-dihydroxydiphenyl, etc.) Nylene group, etc.].

The diamine residue represented by A ^5, for example, ethylenediamine, diethylene diamine, N, N-dimethylethylenediamine, _{C 2-4} alkylenediamine, such as propylene diamine; 1,3- piperazine, 1,4-piperazine, 2- Piperazines such as methyl-1,4-piperazine, 2,5-dimethyl-1,4-piperazine, 2,6-dimethyl-1,4-piperazine; 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, etc. C _4-8 cycloalkyl diamine; phenylene diamine (eg, 1,3-phenylene diamine, 1,4-phenylene diamine, etc.); toluene diamine (eg, 2,4-diaminotoluene, 2,5-diaminotoluene, 3 , 5-Diethyl-2,4-diaminotoluene, 3,5-diethyl-2,4 Xylylenediamine (eg, 1,3-xylylenediamine, 1,4-xylylenediamine, etc.); diaminodiphenylmethane (eg, 4,4′-diaminodiphenylmethane, 2,2′-diethyl-4) , 4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5 5′-tetraethyl-4,4′-diaminodiphenylmethane, etc.); diaminodiphenyl ether (eg, 4,4′-diaminodiphenyl ether, 2,2′-dimethyl-4,4′-diaminodiphenyl ether, etc.); diaminodiphenyl sulfone (eg, 4,4'-diaminodiphenylsulfone, 3,3-dimethyl-4,4'-diaminodiph Vinyl sulfonic, 3,3-diethyl-4,4'-diaminodiphenylsulfone, etc.); diaminodiphenyl sulfide (for example, residues and 4,4'-diaminodiphenyl sulfide.

As the arylene group represented by A ^5, hydroquinone residue, phenylene group, such as resorcinol residues, bisphenols (e.g., bisphenol A, bisphenol F, bisphenol -AD, 2,2'-dihydroxy-diphenylmethane Dihydroxydiarylalkanes such as 2,2′-diethyl-4,4′-dihydroxydiphenylmethane; dihydroxydiaryl ethers such as bis (4-hydroxyphenyl) ether and 4,4′-dihydroxydiphenylether; Dihydroxy diaryl sulfides such as dihydroxy diphenyl sulfide: dihydroxy diaryl sulfones such as 4,4′-dihydroxydiphenyl sulfone; bisphenols exemplified above) residues and the like.

（式中、Ａ^１〜Ａ^５は、上記式（３）と同じである。） Preferred phosphoric ester amides include compounds in which n is 0 or 1, particularly n is 1 in formula (3). The compound in which n is 1 is represented by the following formula (6).

(In the formula, A ^{1 to} A ⁵ are the same as the above formula (3).)

Specific examples of the phosphoric ester amide include piperazine diyl phosphate such as 1,4-piperazinediyltetraphenyl phosphate, 1,4-piperazinediyltetracresylphosphate, 1,4-piperazinediyltetraxylphosphate; ethylenediaminediyltetra C _2-6 alkylene diamine diyl phosphate such as phenyl phosphate, N, N′-dimethylethylenediamine diyl tetraphenyl phosphate; 1,3-phenylenediamine diyl tetraphenyl phosphate, 1,3-xylylenediamine diyl tetraphenyl phosphate, resorcinol tri phenyl phosphate diphenyl amide, hydroquinone triphenyl phosphate diphenylamide C _6-10 may have a substituent such as aryl Emissions diamine diyl phosphate; bisphenol A triphenyl phosphate closed butyl amide, bisphenol phosphate C _6-10 aryl amide, such as bisphenol A triphenyl phosphate diphenyl amide; diphenyl phosphate closed butyl amide, diphenyl phosphate methylphenyl amide, diphenyl phosphate such as diphenyl phosphate diphenylamide C _6-10 arylamides; piperidinophosphates such as piperidinodiphenyl phosphate, piperidinodicresyl phosphate, piperidinodoxysilyl phosphate; pipecolinodiphenyl phosphate, pipecolinodicresyl phosphate, pipecolinodoxysilyl phosphate And pipecoline phosphate.
These phosphoric ester amides can be used alone or in combination of two or more.

The production method of the phosphoric ester amide used in the present invention is not particularly limited, but is described in JP-A-10-175985, Jornal of Chem. Soc. C, 3614 (1971), JP-A-8-59888, JP-A-63-235363, and the like.
Commercially available phosphoric ester amides can be obtained under the trade name “Phosphate ester amide flame retardant SP series (for example, SP-601, SP-703, etc.)” (manufactured by Shikoku Kasei Kogyo Co., Ltd.).

The mass ratio of component (B) to the total mass of components (A) to (C) or components (A) to (D) is 0.2 to 8% by mass. If it is less than 0.2% by mass, the flame retardancy is lowered. On the other hand, if it exceeds 8% by mass, flame retardancy is not improved and phosphoric ester amide is bleed. Preferably, it is 0.3-2 mass%. More preferably, it is 0.5-1.8 mass%.
In the composition of this invention, since the addition amount of phosphoric ester amide is small, the bleed-out of this component can be suppressed.

[式中、Ｒ^１〜Ｒ^４はそれぞれ水素原子又は下記式（２）の有機基を表す。Ｒ^１〜Ｒ^４の少なくとも１つは下記式（２）の有機基である。

（式中、Ｒ^５は炭素数１〜１７のアルキル基、炭素数５〜１０のシクロアルキル基、フェニル基又は炭素数７〜１５のフェニルアルキル基を表し、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９はそれぞれ炭素数１〜４からなるアルキル基を表す。Ｒ^１０は水素原子、又は炭素数１〜１２の直鎖あるいは分岐鎖のアルキル基を表す。）] (C) NOR type hindered amine stabilizer A NOR type hindered amine stabilizer represented by the following formula (1) is used.

[Wherein, R ^{1 to} R ⁴ each represents a hydrogen atom or an organic group of the following formula (2). At least one of R ^{1 to} R ⁴ is an organic group of the following formula (2).

(In the formula, R ⁵ represents an alkyl group having 1 to 17 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a phenyl group, or a phenylalkyl group having 7 to 15 carbon atoms, and R ⁶ , R ⁷ , R ⁸ and R ⁹ represents an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms.

Of the alkyl groups having 1 to 17 carbon atoms which are R ⁵ , a methyl group or an octyl group is preferable.
Of the cycloalkyl groups having 5 to 10 carbon atoms, a cyclohexyl group is preferred.
Moreover, a phenyl group is preferable among a phenyl group or a C7-15 phenylalkyl group.

Of the alkyl groups having 1 to 4 carbon atoms which are R ^{6 to} R ⁹ , a methyl group is preferable.
Among linear or branched alkyl group having 1 to 12 carbon atoms is R ^10, n-butyl group are preferable.

In formula (1), it is desirable that R ¹ , R ² , and R ³ are organic groups of formula (2), or that R ¹ , R ² , and R ⁴ are organic groups of formula (2). .
Specifically, N, N ′, N ″ -tris {2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) n-butylamino] -sym -Triazin-6-yl} -3,3'-ethylenediiminodipropylamine, N, N ', N "-tris {2,4-bis [(1-octyloxy-2,2,6,6- Tetramethylpiperidin-4-yl) n-butylamino] -sym-triazin-6-yl} -3,3′-ethylenediiminodipropylamine, N, N ′, N ″ -tris {2,4-bis [(1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) n-butylamino] -sym-triazin-6-yl} -3,3′-ethylenediiminodipropylamine It can be illustrated.

  The NOR type hindered amine stabilizer used in the flame retardant polyolefin resin composition of the present invention may be used alone or in combination of two or more.

  The mass ratio of component (C) to the total mass of components (A) to (C) or components (A) to (D) is 0.2 to 2.0 mass%. If it is less than 0.2% by mass, the flame retardancy is lowered. On the other hand, if it exceeds 2.0 mass%, the flame retardancy is not improved so much and bleeding occurs. Preferably, it is 0.3-1.8 mass%. More preferably, it is 0.5-1.5 mass%.

(D) Inorganic flame retardant As the inorganic flame retardant, silica (silicon dioxide), synthetic amorphous silica (silicon dioxide), aluminum silicate, magnesium silicate, calcium silicate, zirconium silicate, diatomaceous earth, etc. Silicon hydroxide: metal hydroxide such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, zinc hydroxystannate, tin oxide hydrate, borax Metal oxides such as aluminum oxide, magnesium oxide, barium oxide, titanium oxide, zinc oxide, tin oxide, zirconium oxide, molybdenum oxide, antimony oxide, zirconium-antimony composite oxide; zinc carbonate, calcium carbonate, barium carbonate, carbonic acid Magnesium, magnesium carbonate-calcium etc. Metal carbonate compounds; metal sulfate compounds such as aluminum sulfate and barium sulfate; boric acid compounds such as zinc borate, zinc metaborate, barium metaborate and aluminum borate; stannic acids such as zinc stannate and zinc hydroxystannate Compound: Examples include inorganic compound composites such as alumina hydrate, zeolite, sepiolite, hydrotalcite, hydroxyapatite, diatomaceous earth.

  Of these, hydrotalcite, dolomite compounds, magnesium oxide, zinc borate and zinc stannate are preferred. In particular, hydrotalcite and dolomite compounds are particularly preferable.

A hydrotalcite is a compound which consists of magnesium and aluminum, Comprising: For example, the compound represented by a following formula can be mentioned.
Mg _1-X Al _X (OH) ₂ (A ^q− ) _{X / q} · aH ₂ O
(Wherein q is 1 or 2, A ^q− is a q-valent anion, ie, (CO ₃ ) ²⁻ or (ClO ₄ ) ⁻ , X is 0 <X ≦ 0.5, and a is 0 <A real number satisfying a ≦ 1.)

Typical examples of hydrotalcite include the following.
Mg _0.750 Al _0.250 (OH) ₂ (CO ₃ ) _0.125 · 0.5H ₂ O
Mg _0.692 Al _0.308 (OH) ₂ (CO ₃ ) _0.154 · 0.1H ₂ O
_{Mg 0.683 Al 0.317 (OH) 2} (CO 3) 0.159 · 0.5H 2 O
Mg _0.667 Al _0.333 (OH) ₂ (CO ₃ ) _0.167 · 0.1H ₂ O
Mg _0.750 Al _0.250 (OH) ₂ (ClO ₄ ) _0.250 · 0.5H ₂ O
Mg _0.692 Al _0.308 (OH) ₂ (ClO ₄ ) _0.308 · 0.1H ₂ O
Mg _0.667 Al _0.333 (OH) ₂ (ClO ₄ ) _0.333 · 0.1H ₂ O
A commercially available hydrotalcite can be used.

  There is no special restriction | limiting as a dolomite type compound, The dolomite currently produced widely and used for a wall material, a refractory for iron manufacture, etc. can be used. Further, as the dolomite compound, synthetic dolomite whose chemical composition is composed of a double salt of calcium carbonate and magnesium carbonate can be used.

  The composition of natural dolomite and / or synthetic dolomite used in the present invention is only required to be mixed in a certain ratio of calcium and magnesium, and the weight ratio of calcium and magnesium is 5 to 95 to 95 to 5 in terms of CaO to MgO. It is preferable that When natural dolomite and / or synthetic dolomite outside this ratio range is used, there is a possibility that sufficient flame retardancy may not be obtained.

  Further, in the present invention, these natural and / or synthetic dolomite can be fired, dehydrated, etc., and modified dolomite derivatives can be used without greatly changing the metal element composition. Specific examples thereof include dolomite cement obtained by heating dolomite at 700 to 800 ° C., light-burned dolomite obtained by heating at 900 to 1000 ° C., and dead-burned dolomite hard-fired at a high temperature of 1600 to 1800 ° C., Examples include bituminous slaked lime and synthetic magdro clinker that are digested by adding water to light-burned dolomite.

Furthermore, natural minerals and synthetic compounds such as akermanite (Ca ₂ MgSi ₂ O ₇ ), diopside [CaMg (SiO ₃ ) ₂ ], and various slags in which the ratio of calcium to magnesium is in the same range as the synthetic dolomite described above. Derivatives obtained by modifying salts in the same manner can also be used. Further, any mixture thereof may be used.
These dolomite compounds are industrially widely produced in large quantities and are used in a wide range of industries such as steelmaking, pottery, building materials, agriculture, etc., so they can be obtained easily and inexpensively with stable quality. is there.

  There are no particular restrictions on magnesium oxide, zinc borate, and zinc stannate, and commercially available products can be used.

The average particle size (D ₅₀ ) of the component (D) is 20 μm or less, preferably 10 μm or less, particularly preferably 1 μm or less.
The average particle diameter (D ₅₀ ) is also called a median diameter and is a value of a particle diameter corresponding to 50% cumulative.
Moreover, in order to improve compatibility with a polyolefin resin, a dispersibility, etc., what surface-treated the component (D) with the surface treating agent can also be used. Examples of the surface treatment agent include organic acids and organic acid metal salts. These compounds may be used alone or in any mixture.

  The mass ratio of the component (D) to the total mass of the components (A) to (D) is 0.2 to 5 mass%. If it is less than 0.2% by mass, the flame retardancy is lowered. When it exceeds 5 mass%, flame retardancy will fall. Preferably, it is 0.3-2 mass%. More preferably, it is 0.5-1.8 mass%.

In the present invention, in addition to the above components, conventionally known additives and other blends can be added or blended as necessary within a range that does not impair the purpose of the present invention.
For example, phosphorous compounds, phenolic compounds, sulfur compounds, etc. as antioxidants, weathering agents, various weathering agents such as benzophenone, salicylate, benzotriazole, hindered amines, etc., antistatic agents, anions , Cationic, nonionic, amphoteric and other antistatic agents as lubricants, fatty acids, fatty acid amides, fatty acid metal salts, fatty acid esters, hydrocarbons, etc., nucleating agents as metal salts, sorbitols, etc. As the filler, talc, calcium carbonate, barium sulfate, glass fiber, mica, wollastonite and the like can be used. Furthermore, metal deactivators, colorants, blooming inhibitors, surface treatment agents, and the like can be used.

  The resin composition of this invention can be manufactured by melt-kneading said each component by arbitrary methods. For example, a high-speed stirrer represented by a Henschel mixer, a monoaxial or biaxial continuous kneader, a Banbury mixer, a roll mixer, or the like may be used alone or in combination.

The thin molded article of the present invention can be obtained by molding the above-described resin composition by a known molding method, for example, extrusion molding or injection molding.
For example, in the case of a film, the flame retardant resin composition can be formed by being uniformly extruded into a film shape by commonly used inflation, T-die method or the like, cooled with a normal chill roll, and then wound up. The film may be uniaxially or biaxially stretched. Moreover, a film can also be shape | molded simply by hot press.

  In the case of fibers, the flame retardant resin composition can be obtained by fiberizing by a known melt spinning method. A monofilament will be described below as an example. A monofilament forming die can be used for melt extrusion, followed by cooling and solidification, followed by stretching at a predetermined temperature and a relaxation heat treatment to form a monofilament. As the stretching method, single-stage stretching or multistage stretching more than two-stage stretching is possible.

The thin molded article comprising the flame retardant resin composition of the present invention has excellent flame retardancy even if it is a thin article having a thickness of less than 0.3 mm. Moreover, even if processed into a fiber, sufficient flame retardancy can be imparted.
It has sufficient strength and does not generate toxic gas during combustion.
The thin molded body includes various forms such as a film (sheet) shape and a tube shape.

The present invention will be described in more detail by way of examples, but the present invention is not limited thereby.
The substances used in the following examples and comparative examples are as follows.
Component (A) Polyolefin polypropylene (F-300SP homopolypropylene MI = 3 (g / 10 min) manufactured by Prime Polymer Co., Ltd.)
-Component (B) phosphoric ester amide In formula (3), n = 1 compound (SP-703 manufactured by Shikoku Kasei Kogyo Co., Ltd.)
・ Component (C) NOR type hindered amine stabilizer Ciba Specialty Chemicals Co., Ltd. FlameStab NOR116FF
・ Component (D) Inorganic flame retardant Hydrotalcite: DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.
Dolomite compound: MC-100B manufactured by Sansha Co., Ltd.
Magnesium oxide: Kyowa Chemical Industry Co., Ltd. Kyowa Mag 3-150
Zinc borate: ALCANEX FRC-150 manufactured by Mizusawa Chemical Co., Ltd.
Zinc stannate: ALCANEX ZHS manufactured by Mizusawa Chemical Co., Ltd.
・ Comparator (phosphate ester)
Phosphate ester represented by the following formula used in JP-A No. 2001-348724 (FP-500, manufactured by Asahi Denka Kogyo Co., Ltd.)

Example 1 Comparative Example 1-3
(1) Preliminary mixing Ingredients (A) to (C) are blended in the composition shown in Table 1, and 0.2 parts by weight of glycerin monostearate (Lion Corporation) is added to 100 parts by weight of these total amounts. GS95P), 0.2 part by weight of tris (2,4-di-t-butylphenyl) phosphite (Asahi Denka Kogyo Co., Ltd., MARK 2112), 0.1 part by weight of pentaerythrityl-tetrakis [ 3- (3,5-di-t-butyl-hydroxyphenyl) propionate (Asa-60 manufactured by Asahi Denka Kogyo Co., Ltd.) was blended and premixed with a Henschel mixer or tumbler.

(2) Melt-kneading The obtained pre-mixture was melt-kneaded under the following conditions using a twin-screw kneader (Ikegai Steel Co., Ltd., PCM45) to produce a composition, and strand cutting was used. Pelletized.
・ Kneading temperature: 210-230 ° C
・ Screw speed 150rpm
・ Combination of mesh 40 and 60 ・ Vent 2 places (one normal pressure vent, one vacuum vent)
・ Discharge rate 40kg / h

(3) Production of film The obtained composition pellet 3g was sandwiched between 300 × 300 mm aluminum plates mirror-finished, and pressed with a hot press machine at 230 ° C. and 30 tons to obtain a film having a thickness of 100 μm.

(4) Fabrication of fiber The obtained composition pellets were melted at 230 ° C. using a capillary meter with a barrel diameter of 9.55 mm (Capillograph 1D manufactured by Toyo Seiki Co., Ltd.) and extruded from a capillary with an inner diameter of 1 mm and a length of 10 mm. A fiber (average diameter: 0.25 mm) was produced by spinning at 5 mm / min and a take-up speed of 5 m / min, and performing winding drawing.

(5) Flame-retardant evaluation About the produced film and fiber, it evaluated by the following method.
-Oxygen index of film An oxygen index test was conducted according to the V-type test piece test method shown in JIS-K-7201-2.
Briefly, after a test piece was sandwiched and fixed in a specified U-shaped holder, it was placed in an atmosphere of various oxygen concentrations, an igniter was brought close to the upper end, and the oxygen concentration during continuous combustion after ignition was determined. . The determination of the oxygen index value is the oxygen concentration necessary for the combustion time to continue to burn for 3 minutes or more from the upper benchmark, or for the combustion length to continue to burn for 80 mm or more from the upper benchmark.
-Oxygen index of fiber The oxygen index was measured according to the E-1 test piece test of the test method shown in JIS-L-1091.
Briefly, the fiber is densely wound in a coil shape with a wire having a diameter of 0.8 mm as a core, and the length is made 100 mm, and then the wire is extracted. It was placed in an atmosphere of various oxygen concentrations, and an igniter was brought close to the upper end of the atmosphere, and the oxygen concentration when continuously burning after ignition was determined. The determination of the oxygen index value is the oxygen concentration necessary for the combustion time to continue to burn for 3 minutes or more, or for the combustion length after ignition to continue to burn for 50 mm or more.
The evaluation results are shown in Table 1.

Example 1 is a component (A) / component (B) / component (C) composition. By using the component (B) and the component (C) in combination, high flame retardancy is exhibited even when the amount of the component (B) used is about the same as the additive.
Comparative Examples 1 and 2 are cases where the component (B) or the component (C) is not blended, and the flame retardancy is lowered as compared with Example 1.
The comparative example 3 is a case where a phosphate ester is used instead of the component (B), and the flame retardancy is lowered as compared with Example 1 using the component (B) phosphate ester amide.

Example 2-6
Resin composition pellets, films and fibers were prepared and evaluated in the same manner as in Example 1 except that the components (A) to (D) were blended in the blending composition shown in Table 2.
The evaluation results are shown in Table 2.

Examples 2 to 6 are systems in which the components (A) to (D) are blended, and the case where the component (D) is implemented with various inorganic compounds, each showing high flame retardancy.
By blending the component (D), flame retardancy is further improved as compared with Example 1.
For example, the oxygen index pass value of a thin corrugated tube is 23.5 or more. The oxygen index value of the film molded body close to the corrugated tube molded body of the resin composition of the present invention passes 25 or more. However, it is 23 in the comparative example, which is rejected. Therefore, the resin composition of the present invention has sufficient flame retardancy for use in molded articles in the field of thin materials.

Molded articles comprising the flame retardant resin composition of the present invention are used in the fields of use of polyolefin fibers, polyolefin films, and polyolefin sheets, such as automobile fibers, tents, camping equipment, wall materials, sunshades, rain screens, curtains, and jutans. , Cushions, chairs, cloths, architectural films, curing sheets, parts for electrical materials, flame retardant tapes, corrugated tubes, tubes, sheaths, electric wire coatings, optical fiber coating materials, optical fiber cables and the like.

Claims (7)

A flame retardant resin composition comprising the following components (A) to (C).
(A) Polyolefin resin: 90-99.6% by mass
(B) Phosphate ester amide: 0.2 to 8% by mass
(C) NOR type hindered amine stabilizer represented by the following formula (1): 0.2 to 2% by mass

[Wherein, R ^{1 to} R ⁴ each represents a hydrogen atom or an organic group of the following formula (2). At least one of R ^{1 to} R ⁴ is an organic group of the following formula (2).

(In the formula, R ⁵ represents an alkyl group having 1 to 17 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a phenyl group, or a phenylalkyl group having 7 to 15 carbon atoms, and R ⁶ , R ⁷ , R ⁸ and R ⁹ represents an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms.   Furthermore, the flame-retardant resin composition of Claim 1 which contains 0.2-5 mass% of (D) inorganic type flame retardant with respect to the total amount of said component (A)-(D). The flame retardant resin composition according to claim 1 or 2, wherein the phosphoric ester amide of the component (B) is a compound represented by the following formula (3).

[Wherein, A ^{1 to} A ⁴ each represent —OR ¹¹ (R ¹¹ represents an alkyl group, a cycloalkyl group, or an aryl group, and these groups optionally have a substituent) or —NR ¹² R ¹³ (R ¹² and R ¹³ each represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. These may have a substituent, and R ¹² and R ¹³ are bonded to each other to form a ring. May be formed). A ⁵ represents a diamine residue or an arylenedioxy group, and n represents an integer of 0 to 20. If A ⁵ is not a diamine ^residue, at least one of A 1 to A ^{4 is} a group represented by ^-NR 12 ^{R 13.} ] The flame retardant resin composition according to claim 3, wherein A ^{5 in the} formula (3) is an organic group represented by the following formula (4) or (5).

(Wherein R ¹⁴ and R ¹⁵ each represent a hydrogen atom, an alkyl group, or a cycloalkyl group, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Z ¹ represents an alkylene group, An alkylene group or a divalent aromatic group; Z ² represents a divalent aromatic group.)   The inorganic flame retardant of the component (D) is at least one flame retardant selected from hydrotalcite, dolomite compounds, magnesium oxide, zinc borate and zinc stannate. The flame-retardant resin composition according to claim 1.   A thin molded article having a thickness of less than 0.3 mm, comprising the flame retardant resin composition according to any one of claims 1 to 5. The fiber which consists of a flame-retardant resin composition in any one of Claims 1-5.