JP4356501B2 - Flame retardant fiber and fiber molded body using the same - Google Patents

Description

  The present invention relates to a flame retardant fiber having both excellent flame resistance and excellent weather resistance, and a fiber molded body using the fiber.

In recent years, from the viewpoint of preventing fires or ensuring safety in the event of a fire, it is required to impart flame retardancy to various articles. This is not an exception for fiber molded bodies such as fibers made of thermoplastic resins and nonwoven fabrics made of the fibers (hereinafter also referred to as “fibers”). In particular, many of the fibers used for automobile interior materials, interior materials, filter materials, etc. have been tried to impart flame retardancy by blending flame retardants or treating the surface with flame retardants. Has been made. Flame retardants include halogen compounds, heavy metal compounds, metal hydroxides, phosphorus compounds and the like, and these are used alone or in admixture of two or more.
Of these, chlorine-based or bromine-based halogen compounds and combinations of these with antimony oxide and the like are widely used, and in particular, flame retardant compositions composed of bromine-based halogen compounds and antimony trioxide are excellent in difficulty. Because it has a flammable effect, it is used in a wide range of applications. However, in recent years, awareness of environmental issues has increased, and it has been pointed out that halogen compounds generate harmful gases (hydrogen halides) during combustion and that they can contribute to the generation of dioxins. It was. In addition, it has been pointed out that heavy metals such as antimony oxide can become carcinogenic substances, and use in places where they come into contact with the human body is undesirable for health.

  In addition, since applications such as automobile interior materials, interior materials, and filter materials are often used for a long period of time, it is necessary to prevent a decrease in physical strength due to thermal degradation or ultraviolet degradation. As a method for preventing deterioration, a technique of adding a weathering agent to the fiber used for the application is generally used, but the acidic group generated from the halogen compound or antimony oxide deprives the activity of the weathering agent. The fiber using the flame retardant composition has a problem that the weather resistance is not improved and it cannot withstand long-term use. Therefore, a flame retardant that does not inhibit weather resistance, does not contain heavy metals, and does not generate harmful substances during combustion or processing is strongly desired.

  In order to solve these problems, flame retardants other than halogen compounds and antimony oxide have been studied, but the present situation is that no flame retardant having an excellent flame retardant effect comparable to these can be found. Metal hydroxides and phosphorus compounds can also be used as flame retardants, but in order to give the desired flame retardant effect to fibers etc., the amount used is compared to the amount used of the flame retardant composition. There is a tendency to increase significantly. When a fiber is obtained by spinning using a composition in which a flame retardant is blended with a thermoplastic resin, if the amount of the flame retardant used is large, not only the mechanical strength of the resulting fiber decreases, but also the production itself Has the disadvantage of becoming difficult. Also, the economy is bad.

It has been disclosed that a hindered amine derivative having a specific structure is used as a flame retardant that does not generate harmful substances during combustion or processing (see, for example, Patent Documents 1 to 4). However, the hindered amine derivative also has the same disadvantages as described above because it has poor flame retardancy compared to the flame retardant composition.
Furthermore, it is disclosed that the hindered amine derivative and a phosphorus compound such as aryl phosphite are used in combination in order to enhance the flame retardancy (see, for example, Patent Documents 3 and 4). However, as described above, it could not have sufficient flame retardancy. If arylphosphite is used in a large amount to obtain sufficient flame retardancy, the strength required for fibers will not be exhibited, and arylphosphite has a low boiling point, so it volatilizes under the temperature conditions during spinning. There is a problem that the spinnability is deteriorated, and the bleedout of the aryl phosphite is likely to occur from the obtained fiber and the like, and there is a problem that the quality is deteriorated and the sustainability of the flame retardancy is lowered.

  In addition, phosphate esters such as aryl phosphites often contain catalyst residues used during production. When fibers are obtained using olefin resins, these residues promote the decomposition of olefin resins. Therefore, there is a problem that the strength of the fiber or the like is reduced. Moreover, the working environment at the time of manufacture is not only deteriorated by a unique odor, but also the obtained fiber has a problem that it is odorous.

  The use of a specific cyclic phosphazene compound as a flame retardant is disclosed (for example, see Patent Document 5). The cyclic phosphazene compound is easy to handle and does not cause environmental problems, and is excellent in thermal stability and hydrolysis resistance, but when used alone, the flame retardant performance is inferior compared to the flame retardant composition, It has the same disadvantages as described above. For this reason, in order to mix | blend this cyclic phosphazene compound and to have sufficient flame retardance, it is required to mix | blend the quantity of 10 weight% or more. Applications of the thermoplastic resin composition containing a large amount of flame retardant are limited to heat compression molded products and the like, and there is a problem that it is difficult to mold extremely thin materials such as fibers. As a method for imparting flame retardancy to fibers or the like, a method of immersing fibers or the like in a solution comprising the cyclic phosphazene compound can be employed. However, in this method, the cyclic phosphazene compound is simply adhered to the surface of a fiber or the like, and the cyclic phosphazene compound is peeled off by post-processing, post-treatment and continuous use, so that the flame retardancy performance is extremely long. It ’s bad.

JP-T-2002-507238 JP 2001-254225 A JP 2002-115118 A JP 2001-348724 A JP 2001-192392 A

  The problem to be solved by the present invention is that the adverse effects on the environment and the human body, such as the generation of harmful substances, are extremely low, have both excellent flame resistance and excellent weather resistance, and do not impair spinnability and fiber strength. It is to provide a flammable fiber and a fiber molded body obtained by the fiber.

  As a result of intensive studies in order to solve the above problems, the present inventors have blended a thermoplastic resin with a hindered amine derivative having a specific structure and a phosphazene compound having a specific structure at a specific ratio. The inventors have found that the above problems can be solved by obtaining fibers having a specific fineness, and have completed the present invention based on this finding.

[ 式中、ｍは３〜１０の整数であり、２個のＱはアルコキシ基、アリールオキシ基及びアミノ基からなる群からそれぞれ独立して選ばれる基を示す。]

[ 式中、ｎは３〜１０の整数であり、９個のＱはアルコキシ基、アリールオキシ基及びアミノ基からなる群からそれぞれ独立して選ばれる基を示す。]

[ 式中、Ｒ_１は炭素数 １〜１８ のアルキル基、炭素数 ５〜１２ のシクロアルキル基、炭素数 ７〜１８ の二環式または三環式の炭化水素基、炭素数 ７〜１５ のフェニルアルキル基を示し、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は独立して炭素数 １〜４ のアルキル基を示すか、Ｒ_２とＲ_３及び／またはＲ_４とＲ_５が結合したペンタメチレン基を示し、Ｒ_６は炭素数 １〜４ のアルコキシル基、炭素数 ６〜１２ のアリールオキシ基、炭素数 １〜１８ のアミノ基、下記一般式（IV）を示し、Ａは酸素原子または Ｎ−Ｒ_７ （式中、Ｒ_７は水素原子、炭素数 １〜１２ の直鎖または分岐鎖のアルキル基を示す。）を示す。]

[ 式中、Ｒ_１は炭素数 １〜１８ のアルキル基、炭素数 ５〜１２ のシクロアルキル基、炭素数 ７〜１８ の二環式または三環式の炭化水素基、炭素数 ７〜１５ のフェニルアルキル基を示し、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は独立して炭素数 １〜４ のアルキル基を示すか、Ｒ_２とＲ_３及び／またはＲ_４とＲ_５が結合したペンタメチレン基を示し、Ａは酸素原子または次式 Ｎ−Ｒ_７ （式中、Ｒ_７は水素原子、炭素数 １〜１２の直鎖または分岐鎖のアルキル基を示す。）を示す。] The present invention is constituted by the following.
(1) Flame retardancy made of thermoplastic resin containing flame retardant (excluding decabromodiphenyl oxide, bis (2,3-dibromopropyl) ether of tetrabromobisphenol A, ethylene bis-tetrabromophthalimide) And at least one phosphazene derivative selected from a cyclic phosphazene derivative represented by the following general formula (I) and a chain phosphazene derivative represented by the following general formula (II): A hindered amine derivative containing a group represented by the formula: wherein the fiber contains 0.25 to 5.0% by weight of the phosphazene derivative and 0.025 to 3.0% by weight of the hindered amine derivative, and a flame retardant in the fiber It ranges total addition amount of 1-6% by weight of component, to wherein the fineness of the fiber is 0.01 to 50 dtex Flame-retardant fiber.

[Wherein, m is an integer of 3 to 10, and two Q's each independently represent a group selected from the group consisting of an alkoxy group, an aryloxy group and an amino group. ]

[Wherein, n is an integer of 3 to 10, and nine Qs each independently represent a group selected from the group consisting of an alkoxy group, an aryloxy group and an amino group. ]

[Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon group having 7 to 18 carbon atoms, or 7 to 15 carbon atoms. R ₂ , R ₃ , R ₄ and R ₅ independently represent a C 1-4 alkyl group, or R ₂ and R ₃ and / or R ₄ and R ₅ bonded penta R ₆ represents an alkoxyl group having 1 to 4 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an amino group having 1 to 18 carbon atoms, the following general formula (IV), and A represents an oxygen atom or N—R ₇ (wherein R ₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms). ]

[Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon group having 7 to 18 carbon atoms, or 7 to 15 carbon atoms. R ₂ , R ₃ , R ₄ and R ₅ independently represent a C 1-4 alkyl group, or R ₂ and R ₃ and / or R ₄ and R ₅ bonded penta Represents a methylene group, and A represents an oxygen atom or the following formula N—R ₇ (wherein R ₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms). ]

( 2 ) The flame-retardant fiber according to (1), wherein the thermoplastic resin is a resin selected from a copolymer mainly composed of polyolefin and olefin.

( 3 ) The flame-retardant fiber according to any one of (1) to ( 2 ), wherein the fiber is a composite fiber.

[ 式中、ｍは３〜１０の整数であり、２個のＱはアルコキシ基、アリールオキシ基及びアミノ基からなる群からそれぞれ独立して選ばれる基を示す。]

[ 式中、ｎは３〜１０の整数であり、９個のＱはアルコキシ基、アリールオキシ基及びアミノ基からなる群からそれぞれ独立して選ばれる基を示す。]

[ 式中、Ｒ_１は炭素数 １〜１８ のアルキル基、炭素数 ５〜１２ のシクロアルキル基、炭素数 ７〜１８ の二環式または三環式の炭化水素基、炭素数 ７〜１５ のフェニルアルキル基を示し、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は独立して炭素数 １〜４ のアルキル基を示すか、Ｒ_２とＲ_３及び／またはＲ_４とＲ_５が結合したペンタメチレン基を示し、Ｒ_６は炭素数 １〜４ のアルコキシル基、炭素数 ６〜１２ のアリールオキシ基、炭素数 １〜１８ のアミノ基、下記一般式（IV）を示し、Ａは酸素原子または Ｎ−Ｒ_７ （式中、Ｒ_７は水素原子、炭素数 １〜１２ の直鎖または分岐鎖のアルキル基を示す。）を示す。]

[ 式中、Ｒ_１は炭素数 １〜１８ のアルキル基、炭素数 ５〜１２ のシクロアルキル基、炭素数 ７〜１８ の二環式または三環式の炭化水素基、炭素数 ７〜１５ のフェニルアルキル基を示し、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は独立して炭素数 １〜４ のアルキル基を示すか、Ｒ_２とＲ_３及び／またはＲ_４とＲ_５が結合したペンタメチレン基を示し、Ａは酸素原子または次式 Ｎ−Ｒ_７ （式中、Ｒ_７は水素原子、炭素数 １〜１２の直鎖または分岐鎖のアルキル基を示す。）を示す。] ( 4 ) A fiber molded body using the fiber according to any one of (1) to ( 3 ).
( 5 ) Flame retardant comprising a thermoplastic resin containing a flame retardant (excluding decabromodiphenyl oxide, bis (2,3-dibromopropyl) ether of tetrabromobisphenol A, ethylene bis-tetrabromophthalimide) A method for producing a fiber, wherein the flame retardant is at least one phosphazene derivative selected from a cyclic phosphazene derivative represented by the following general formula (I) and a chain phosphazene derivative represented by the following general formula (II): A hindered amine derivative containing the group represented by (III), 0.25 to 5.0% by weight of the phosphazene derivative in the fiber, 0.025 to 3.0% by weight of the hindered amine derivative, and a flame retardant in the fiber It contains a flame retardant component such that the total amount of the components is in the range of 1-6 wt%, fineness of 0.01 to 50 dt Method for producing a flame-retardant fiber characterized by the production of fibers of x.

[Wherein, m is an integer of 3 to 10, and two Q's each independently represent a group selected from the group consisting of an alkoxy group, an aryloxy group and an amino group. ]

[Wherein, n is an integer of 3 to 10, and nine Qs each independently represent a group selected from the group consisting of an alkoxy group, an aryloxy group and an amino group. ]

[Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon group having 7 to 18 carbon atoms, or 7 to 15 carbon atoms. R ₂ , R ₃ , R ₄ and R ₅ independently represent a C 1-4 alkyl group, or R ₂ and R ₃ and / or R ₄ and R ₅ bonded penta R ₆ represents an alkoxyl group having 1 to 4 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an amino group having 1 to 18 carbon atoms, the following general formula (IV), and A represents an oxygen atom or N—R ₇ (wherein R ₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms). ]

[Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon group having 7 to 18 carbon atoms, or 7 to 15 carbon atoms. R ₂ , R ₃ , R ₄ and R ₅ independently represent a C 1-4 alkyl group, or R ₂ and R ₃ and / or R ₄ and R ₅ bonded penta Represents a methylene group, and A represents an oxygen atom or the following formula N—R ₇ (wherein R ₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms). ]

The flame-retardant fiber of the present invention and the fiber molded body using the same can extremely reduce substances harmful to the human body and the environment that are generated at the time of production, at the time of fire and at the time of incineration. In addition, the hindered amine derivative having a specific structure and the phosphazene derivative having a specific structure, which are flame retardant components constituting the flame retardant fiber of the present invention, are compatible with each other, and excellent flame retardancy in a small amount due to their synergistic effect. Since the performance can be exhibited, the productivity is excellent, the cost can be reduced, and the decrease in physical strength can be remarkably reduced. In addition, since the weather resistance is also excellent, it is possible to maintain physical strength for a long period of time.
As described above, the flame-retardant fiber of the present invention and the fiber molded body using the same are suitable for long-term use because they have a high flame-retardant performance and are less harmful to the environment. It can be used widely and suitably for various products such as materials, interior materials and filter materials.

Hereinafter, the flame-retardant fiber of the present invention will be described in detail. In the present invention, the main component refers to the most abundant component.
In the flame-retardant fiber of the present invention, a hindered amine derivative having a specific structure and a phosphazene derivative having a specific structure are blended in a specific ratio.

[ 式中、ｍは３〜１０の整数であり、２個のＱはアルコキシ基、アリールオキシ基及びアミノ基からなる群からそれぞれ独立して選ばれる基を示す。]

[ 式中、ｎは３〜１０の整数であり、９個のＱはアルコキシ基、アリールオキシ基及びアミノ基からなる群からそれぞれ独立して選ばれる基を示す。]
前記一般式（Ｉ）及び（II）で示されるホスファゼン誘導体は、定義された範囲内のものであれば、格別の制限はない。尚、置換基Ｑとしてのアルコキシ基、アリールオキシ基及びアミノ基の例としては、次のようなものを挙げることができる。 The phosphazene derivative used for the flame-retardant fiber of the present invention is at least one selected from a cyclic phosphazene derivative represented by the following general formula (I) and a chain phosphazene derivative represented by the following general formula (II). is there.

[Wherein, m is an integer of 3 to 10, and two Q's each independently represent a group selected from the group consisting of an alkoxy group, an aryloxy group and an amino group. ]

[Wherein, n is an integer of 3 to 10, and nine Qs each independently represent a group selected from the group consisting of an alkoxy group, an aryloxy group and an amino group. ]
The phosphazene derivative represented by the general formulas (I) and (II) is not particularly limited as long as it is within the defined range. Examples of the alkoxy group, aryloxy group, and amino group as the substituent Q include the following.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and an iso-butoxy group, and the number of carbon atoms is preferably 1-8.
Examples of the aryloxy group are unsubstituted, methyl, ethyl, n-propyl, iso-propyl, tert-butyl, tert-octyl, methoxy, ethoxy, and 2,3-dimethyl. A phenyloxy group substituted with a group, 2,4-dimethyl group, 2,5-dimethyl group, 2,6-dimethyl group, 3,5-dimethyl group, phenyl group, and the like. Further, examples of the aryl include naphthyl.

Examples of the amino group include linear or branched monoalkylamino groups such as NH ₂ group, methylamino group, and ethylamino group, linear or branched dialkylamino groups such as dimethylamino group, and diethylamino group. Can be mentioned.
The phosphazene derivative may contain a by-product having a halogen remaining as an unreacted substance in the production process at the position Q, but the present invention provides a flame-retardant fiber that generates extremely little harmful gas. Therefore, it is desirable that the total halogen content in the phosphazene derivative is 0.05% by weight or less.

  Specific examples of the cyclic phosphazene derivative represented by the general formula (I) used in the flame-retardant fiber of the present invention include 1,1,3,3,5,5-hexa (methoxy) cyclotriphosphazene, 1, 1,3,3,5,5-hexa (ethoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (n-propoxy) cyclotriphosphazene, 1,1,3,3,5 5-hexa (iso-propoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (n-butoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (iso-) Butoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (phenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (p-tolyloxy) cyclotriphosphazene, 1, , 3,3,5,5-hexa (m-tolyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (o-tolyloxy) cyclotriphosphazene, 1,1,3,3,5 , 5-Hexa (p-anisyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (m-anisyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (o) -Anisyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-ethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-n-propylphenoxy) ) Cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-iso-propylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-tert) Butylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-tert-octylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (2,3- Dimethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (2,4-dimethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (2,5- Dimethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (2,6-dimethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexaaminocyclotriphosphazene, 1,1,3,3,5,5-hexa (4-phenylphenoxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (pheno Xyl) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,5- Tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (iso-propoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (n-butoxy) -1, 3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (iso-butoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (methoxy)- 1,3,5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (m-tolyloxy) cycl Triphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (o-tolyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (p -Anisyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (m-anisyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5 -Tris (o-anisyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1 , 3,5-tris (m-tolyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (o-tolyloxy) cyclo Riphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (p-anisyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (m -Anisyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (o-anisyloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3 , 5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (m-tolyloxy) cyclotriphosphazene, 1,3,5-tris ( n-propoxy) -1,3,5-tris (o-tolyloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (p- Anisyloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (m-anisyloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1, 3,5-tris (o-anisyloxy) cyclotriphosphazene, 1,3,5-tris (iso-propoxy) -1,3,5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (N-butoxy) -1,3,5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (iso-butoxy) -1,3,5-tris (p-tolyloxy) cyclotriphosphazene 1,3,5-tris (methoxy) -1,3,5-tris (4-tert-butylphenoxy) cyclotriphosphazene, 1,3,5 Tris (methoxy) -1,3,5-tris (4-tert-octylphenoxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (4-tert-butyl Phenoxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (4-tert-octylphenoxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1 , 3,5-tris (4-phenylphenoxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (4-phenylphenoxy) cyclotriphosphazene, 1,3,5- Tris (n-propoxy) -1,3,5-tris (4-phenylphenoxy) cyclotriphosphazene, 1,3,5-tris (iso-propyl) Poxy) -1,3,5-tris (4-phenylphenoxy) cyclotriphosphazene, 1,3,5-tris (n-butoxy) -1,3,5-tris (4-phenylphenoxy) cyclotriphosphazene, 1,3,5-tris (iso-butoxy) -1,3,5-tris (4-phenylphenoxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (methoxy) cyclotri Phosphazene, 1,1-diamino-3,3,5,5-tetrakis (ethoxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (n-propoxy) cyclotriphosphazene, 1, 1-diamino-3,3,5,5-tetrakis (iso-propoxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetra Kis (n-butoxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (iso-butoxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis ( Phenoxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (p-tolyloxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (m-tolyloxy) Cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (o-tolyloxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (p-anisyloxy) cyclotri Phosphazene, 1,1-diamino-3,3,5,5-tetrakis (m-anisyloxy) cyclotriphosphazene, 1,1- Amino-3,3,5,5-tetrakis (o-anisyloxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (4-phenyl phenoxy) cyclotriphosphazene, and the like.

  Specific examples of the chain phosphazene derivative represented by the general formula (II) used in the flame-retardant fiber of the present invention include 1,1,3,3,5,5-hexa (methoxy) triphosphazene, 1, 1,3,3,5,5-hexa (ethoxy) triphosphazene, 1,1,3,3,5,5-hexa (n-propoxy) triphosphazene, 1,1,3,3,5,5- Hexa (iso-propoxy) triphosphazene, 1,1,3,3,5,5-hexa (n-butoxy) triphosphazene, 1,1,3,3,5,5-hexa (iso-butoxy) triphosphazene 1,1,3,3,5,5-hexa (phenoxy) triphosphazene, 1,1,3,3,5,5-hexa (p-tolyloxy) triphosphazene, 1,1,3,3,5 , 5-Hexa (m-tolyloxy) to Phosphazene, 1,1,3,3,5,5-hexa (o-tolyloxy) triphosphazene, 1,1,3,3,5,5-hexa (p-anisyloxy) triphosphazene, 1,1,3 3,5,5-hexa (m-anisyloxy) triphosphazene, 1,1,3,3,5,5-hexa (o-anisyloxy) triphosphazene, 1,1,3,3,5,5-hexa ( 4-ethylphenoxy) triphosphazene, 1,1,3,3,5,5-hexa (4-n-propylphenoxy) triphosphazene, 1,1,3,3,5,5-hexa (4-iso-) Propylphenoxy) triphosphazene, 1,1,3,3,5,5-hexa (4-tert-butylphenoxy) triphosphazene, 1,1,3,3,5,5-hexa (4-tert-octylfe) Xyl) triphosphazene, 1,1,3,3,5,5-hexa (2,3-dimethylphenoxy) triphosphazene, 1,1,3,3,5,5-hexa (2,4-dimethylphenoxy) Triphosphazene, 1,1,3,3,5,5-hexa (2,5-dimethylphenoxy) triphosphazene, 1,1,3,3,5,5-hexa (2,6-dimethylphenoxy) triphosphazene 1,1,3,3,5,5-hexaaminotriphosphazene, 1,1,3,3,5,5-hexa (4-phenylphenoxy) triphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (phenoxy) triphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (phenoxy) triphosphazene, 1,3,5-tris (n-propoxy) − 1,3,5-tris (phenoxy) triphosphazene, 1,3,5-tris (iso-propoxy) -1,3,5-tris (phenoxy) triphosphazene, 1,3,5-tris (n-butoxy) ) -1,3,5-tris (phenoxy) triphosphazene, 1,3,5-tris (iso-butoxy) -1,3,5-tris (phenoxy) triphosphazene, 1,3,5-tris (methoxy) ) -1,3,5-tris (p-tolyloxy) triphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (m-tolyloxy) triphosphazene, 1,3,5-tris (Methoxy) -1,3,5-tris (o-tolyloxy) triphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (p-anisyloxy) triphosphazene 1,3,5-tris (methoxy) -1,3,5-tris (m-anisyloxy) triphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (o-anisyloxy) ) Triphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (p-tolyloxy) triphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (m -Tolyloxy) triphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (o-tolyloxy) triphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (P-anisyloxy) triphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (m-anisyloxy) triphosphazene, 1,3,5-tris (ethoxy) -1, , 5-Tris (o-anisyloxy) triphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (p-tolyloxy) triphosphazene, 1,3,5-tris (n- Propoxy) -1,3,5-tris (m-tolyloxy) triphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (o-tolyloxy) triphosphazene, 1,3 5-tris (n-propoxy) -1,3,5-tris (p-anisyloxy) triphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (m-anisyloxy) tri Phosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (o-anisyloxy) triphosphazene, 1,3,5-tris (iso-propoxy) -1 , 3,5-tris (p-tolyloxy) triphosphazene, 1,3,5-tris (n-butoxy) -1,3,5-tris (p-tolyloxy) triphosphazene, 1,3,5-tris ( iso-butoxy) -1,3,5-tris (p-tolyloxy) triphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (4-tert-butylphenoxy) triphosphazene, , 3,5-tris (methoxy) -1,3,5-tris (4-tert-octylphenoxy) triphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (4 -Tert-butylphenoxy) triphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (4-tert-octylphenoxy) triphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (4-phenylphenoxy) triphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (4-phenylphenoxy) ) Triphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (4-phenylphenoxy) triphosphazene, 1,3,5-tris (iso-propoxy) -1,3 5-tris (4-phenylphenoxy) triphosphazene, 1,3,5-tris (n-butoxy) -1,3,5-tris (4-phenylphenoxy) triphosphazene, 1,3,5-tris (iso) -Butoxy) -1,3,5-tris (4-phenylphenoxy) triphosphazene, 1,1-diamino-3,3,5,5-tetrakis (methoxy) triphosphazene, , 1-Diamino-3,3,5,5-tetrakis (ethoxy) triphosphazene, 1,1-diamino-3,3,5,5-tetrakis (n-propoxy) triphosphazene, 1,1-diamino-3 , 3,5,5-tetrakis (iso-propoxy) triphosphazene, 1,1-diamino-3,3,5,5-tetrakis (n-butoxy) triphosphazene, 1,1-diamino-3,3,5 , 5-tetrakis (iso-butoxy) triphosphazene, 1,1-diamino-3,3,5,5-tetrakis (phenoxy) triphosphazene, 1,1-diamino-3,3,5,5-tetrakis (p -Tolyloxy) triphosphazene, 1,1-diamino-3,3,5,5-tetrakis (m-tolyloxy) triphosphazene, 1,1-diamino-3,3,5 5-tetrakis (o-tolyloxy) triphosphazene, 1,1-diamino-3,3,5,5-tetrakis (p-anisyloxy) triphosphazene, 1,1-diamino-3,3,5,5-tetrakis ( m-anisyloxy) triphosphazene, 1,1-diamino-3,3,5,5-tetrakis (o-anisyloxy) triphosphazene, 1,1-diamino-3,3,5,5-tetrakis (4-phenylphenoxy) ) Triphosphazene and the like.

  In the flame-retardant fiber of the present invention, either one of the cyclic phosphazene derivative and the chain phosphazene derivative may be used, or two or more kinds may be mixed and used, but the cyclic phosphazene derivative should be selected. Is preferred.

[ 式中、Ｒ_１は炭素数 １〜１８ のアルキル基、炭素数 ５〜１２ のシクロアルキル基、炭素数 ７〜１８ の二環式または三環式の炭化水素基、炭素数 ７〜１５ のフェニルアルキル基を示し、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は独立して炭素数 １〜４ のアルキル基を示すか、Ｒ_２とＲ_３及び／またはＲ_４とＲ_５が結合したペンタメチレン基を示し、Ｒ_６は炭素数 １〜４ のアルコキシル基、炭素数 ６〜１２ のアリールオキシ基、炭素数 １〜１８ のアミノ基、下記一般式（IV）を示し、Ａは酸素原子または Ｎ−Ｒ_７ （式中、Ｒ_７は水素原子、炭素数 １〜１２ の直鎖または分岐鎖のアルキル基を示す。）を示す。]

[ 式中、Ｒ_１は炭素数 １〜１８ のアルキル基、炭素数 ５〜１２ のシクロアルキル基、炭素数 ７〜１８ の二環式または三環式の炭化水素基、炭素数 ７〜１５ のフェニルアルキル基を示し、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は独立して炭素数 １〜４ のアルキル基を示すか、Ｒ_２とＲ_３及び／またはＲ_４とＲ_５が結合したペンタメチレン基を示し、Ａは酸素原子または次式 Ｎ−Ｒ_７ （式中、Ｒ_７は水素原子、炭素数 １〜１２の直鎖または分岐鎖のアルキル基を示す。）を示す。] The hindered amine derivative used for the flame-retardant fiber of the present invention contains a group represented by the following general formula (III).

[Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon group having 7 to 18 carbon atoms, or 7 to 15 carbon atoms. R ₂ , R ₃ , R ₄ and R ₅ independently represent a C 1-4 alkyl group, or R ₂ and R ₃ and / or R ₄ and R ₅ bonded penta R ₆ represents an alkoxyl group having 1 to 4 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an amino group having 1 to 18 carbon atoms, the following general formula (IV), and A represents an oxygen atom or N—R ₇ (wherein R ₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms). ]

[Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon group having 7 to 18 carbon atoms, or 7 to 15 carbon atoms. R ₂ , R ₃ , R ₄ and R ₅ independently represent a C 1-4 alkyl group, or R ₂ and R ₃ and / or R ₄ and R ₅ bonded penta Represents a methylene group, and A represents an oxygen atom or the following formula N—R ₇ (wherein R ₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms). ]

[ 式中、Ｒ_１は炭素数 １〜１８ のアルキル基、炭素数 ５〜１２ のシクロアルキル
基、炭素数 ７〜１８ の二環式または三環式の炭化水素基、炭素数 ７〜１５ のフェ
ニルアルキル基を示し、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は独立して炭素数 １〜４ のアルキル
基を示すか、Ｒ_２とＲ_３及び／またはＲ_４とＲ_５が結合したペンタメチレン基を示し、Ｒ
_７は水素原子、炭素数 １〜１２ の直鎖または分岐鎖のアルキル基を示す。]

[ 式中、Ｔ_１ないしＴ_４はそれぞれ独立して水素原子、一般式(Ｖ)から選ばれた基を示す。]
ここで、Ｒ_１同士が架橋反応を起こすこともあるが、該反応物が存在していてもなんら差し支えない。 The hindered amine derivative used for the flame-retardant fiber of the present invention has a structure having both a hindered amine part having weather resistance and a sym-triazine part having flame resistance. The hindered amine derivative having this structure has good compatibility with the phosphazene derivative, and a very excellent synergistic effect can be obtained when used in combination. Among these, a hindered amine derivative having a group represented by the following general formula (V) is preferable, and a hindered amine derivative represented by the following general formula (VI) is more preferable.

[Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon group having 7 to 18 carbon atoms, or 7 to 15 carbon atoms. R ₂ , R ₃ , R ₄ and R ₅ independently represent a C 1-4 alkyl group, or R ₂ and R ₃ and / or R ₄ and R ₅ bonded penta Represents a methylene group, R
₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms. ]

[Wherein, T ₁ to T ₄ each independently represent a hydrogen atom or a group selected from general formula (V). ]
Here, R ₁ may cause a crosslinking reaction, but the reaction product may be present at all.

In the general formula (VI), T ₁ , T ₂ and T ₃ are groups of the general formula (V), or T ₁ , T ₂ and T ₄ are groups of the general formula (V). Some are desirable, 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 and the like.
As the hindered amine derivative used in the flame-retardant fiber of the present invention, any one of the hindered amine derivatives may be used, or two or more may be used as a mixture.

In the flame-retardant fiber of the present invention, the phosphazene derivative is desirably blended in the range of 0.25 to 5.0% by weight, preferably 0.5 to 3.0% by weight. However, it is desirable that it is blended in the range of 0.025 to 3.0% by weight, preferably 0.05 to 2.0% by weight. If each addition amount of the phosphazene derivative and the hindered amine derivative (hereinafter referred to as a flame retardant component) is less than the above range, the obtained fiber cannot be provided with sufficient flame retardancy, while the above range is determined. On the contrary, the flame retardancy tends to be lowered and the cost is increased.
Further, as the total amount of the flame retardant component increases, yarn breakage is likely to occur during spinning, and the physical strength of the fiber decreases, so the total amount added in the fiber is 1 to 6% by weight. It is preferable to use within the range of 1 to 4.5% by weight. Within this range, the spinnability of the fiber is good and the physical properties of the resulting fiber are not adversely affected.

The thermoplastic resin used for the flame-retardant fiber of the present invention is not particularly limited as long as it has fiber forming ability. Specifically, polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyethylene Examples thereof include polyolefins such as (PE) and polypropylene (PP), polyamides such as nylon, polyurethane, polystyrene and acrylic. Further, the thermoplastic resin may be a resin composition containing an elastomer resin as a main component. The main component means the most abundant component. Elastomer resin has the same elastic properties as vulcanized rubber at normal temperature (20-30 ° C) (depending on the soft segment in the molecule), and at high temperatures, existing fiber molding machines can be used in the same way as ordinary thermoplastic resins. It is a polymer material that can be molded as it is (by the hard segment in the molecule). Examples of such elastomer resins include polystyrene elastomers, polyolefin elastomers, polyester elastomers, polyamide elastomers, and polyurethane elastomers.
Among them, a copolymer mainly composed of polyolefin and olefin is preferable because the spinning temperature can be relatively low in order to suppress the volatilization of the flame retardant component, and the flame retardant performance is easily obtained. In particular, the flame retardant component of the present invention has no or very little catalyst residue that promotes the decomposition of the polyolefin, and is therefore optimal for making the polyolefin flame retardant.

  Polyolefins include low-density polyethylene (LDPE), linear low-density polyethylene (L-LDPE), high-density polyethylene (HDPE), polypropylene (PP), and ethylene-propylene because they are easily available and easy to handle. More preferred are polymers and ethylene-propylene-butene copolymers. Moreover, the modified body (For example, a maleic acid modified copolymer and an acrylic acid modified copolymer) which has these as a main component, and a copolymer with styrene and a rubber monomer may be sufficient. These thermoplastic resins may be used alone or as a mixture of two or more.

  In the flame-retardant fiber of the present invention, a conventional additive may be further blended as long as the effects of the present invention are not impaired. For example, an antioxidant, a light stabilizer, a metal deactivator, an ultraviolet absorber, a neutralizer, a nucleating agent, a lubricant, an antibacterial agent, an antistatic agent, a pigment, a plasticizer and a hydrophilic agent may be blended. Moreover, you may mix | blend various fillers, electroconductive powder, another flame retardant, etc. as needed.

  The flame-retardant fiber of the present invention is not particularly limited in its production method. Either the general spinning / drawing method, the spunbond method or the melt blown method can be employed.

  The flame-retardant fiber of the present invention is not particularly limited in its cross-sectional structure, and may be a composite structure using a plurality of thermoplastic resins having different melting points. In particular, a flame retardant fiber having a composite structure in which a thermoplastic resin having a low melting point continuously forms at least a part of the fiber surface in the fiber length direction has improved thermal adhesiveness when obtaining a fiber molded body. The physical strength of the molded product can be kept good. The composite cross section may be any of a sheath core type, a parallel type, and a radial type alternately arranged in a radial manner, and may have a hollow structure, but a thermoplastic resin having a low melting point is used on the sheath side. The conventional sheath-core type and the parallel type having the resin on one side exhibit an effect excellent in thermal adhesiveness between fibers. In addition, those with a radial type structure in which different types of thermoplastic resins are arranged alternately in a radial pattern can be divided into flame retardants by selecting a combination of thermoplastic resins with low compatibility. Can be fiber.

  When the flame retardant fiber of the present invention has a composite structure, the flame retardant component may be blended only in one of them, or the combination ratio and blend amount of the flame retardant component may be different. For example, in a flame-retardant fiber having a sheath-core composite structure, the hindered amine derivative having weather resistance performance may be blended on the sheath side, and the phosphazene derivative having excellent flame retardancy performance may be blended on the core side. From the viewpoint of suppressing the bleed-out of the flame retardant component, it is desirable to add the flame retardant component only to the core side.

  The fineness of the flame-retardant fiber of the present invention is not particularly limited, but if it is in the range of 0.01 to 100 dtex, preferably 0.05 to 50 dtex, the spinnability in the spinning process becomes good and the uniformity is good. A fiber etc. can be obtained.

The flame-retardant fiber of the present invention is a tow state of a long fiber that is not cut after spinning and stretching, even if the flame-retardant fiber of the present invention is subjected to crimping treatment as necessary after being spun and drawn and cut to a predetermined length. However, it may have any form.
When the flame-retardant fiber of the present invention is the former, the fiber length is not particularly limited and can be appropriately selected depending on the application. However, the fiber molded body obtained by thermally fusing the fibers together has a sufficient tensile strength. In order to give it, it is desirable that the fiber length is 2 mm or more. When the flame retardant fiber is used in the card method, although it depends on the fineness, a highly uniform web can be obtained if the length is generally 20 to 76 mm. When the flame retardant fiber is used in a papermaking method or an airlaid method, a length of 2 mm to 20 mm is generally preferable.

  In order to impart functions such as antistatic properties, fiber opening properties, and smoothness to the flame retardant fiber of the present invention, a surfactant can be attached to the surface thereof. As a method for attaching the surfactant to them, a roller method, a dipping method, a pad drying method or the like can be used. In that case, it is preferable to adjust and use the type of surfactant and its concentration according to the application. The step of attaching the surfactant may be performed by any of spinning, drawing, and crimping processes, and if necessary, the surfactant may be attached to the surface after forming a fiber molded body.

  The fiber molded body of the present invention may have any form as long as the flame-retardant fiber of the present invention is used. For example, it may be a woven fabric, a knitted fabric, a non-woven fabric, a filter, etc. using only the flame-retardant fiber of the present invention, and is necessary for the flame-retardant fiber of the present invention as long as it does not significantly impair the effects of the present invention. Depending on the case, it may be a woven fabric, a knitted fabric, a non-woven fabric, a filter, or the like using a blended cotton, a blended fiber, or a mixed fiber with other fibers.

The fiber molded body of the present invention can be produced by a known method. As an example, after cutting the flame-retardant fiber of the present invention into a predetermined length, it is made into a fiber assembly (web) by a dry method such as a card method or a wet method such as a papermaking method, and is bonded by a heating roll or ultrasonic waves. A method of forming a non-woven fabric by fusing with heated air, high-pressure water flow or fiber entanglement with a needle, etc., laminating flame-retardant fibers cut to a predetermined length by the airlaid method, and heat-treating with a heating roll or heated air A method of obtaining a nonwoven fabric, a method of heat-treating a sliver prepared from a flame-retardant fiber cut to a predetermined length by a card method into a fiber molded body, and a knitted fabric using a spun yarn or a continuous yarn The method of obtaining a knitted fabric by processing can be mentioned. In particular, since the flame retardant fiber of the present invention contains a flame retardant component inside, compared with the flame retardant fiber in which the flame retardant component is adhered to the surface by a method such as immersion in a solution, the card method and the high pressure Even with water flow treatment, the flame retardant component removed from the fiber can be extremely suppressed.
In addition, there are a method for obtaining a fiber molded body by a spunbond method or a melt blown method, a method for obtaining a fiber molded body by heat treatment with a superheated roll or heated air without cutting long fiber tows, and the like.

  Specific examples of the other fibers include synthetic fibers such as polyamide, polyester, polyolefin and acrylic, natural fibers such as cotton, wool and hemp, regenerated fibers such as rayon, cupra and acetate, semi-synthetic fibers, polylactic acid fibers, poly Examples thereof include biodegradable fibers such as butylene succinate fiber, pulp, glass fiber, and carbon fiber.

  Since the flame-retardant fiber of the present invention or the fiber molded body of the present invention has excellent flame retardancy and excellent weather resistance, interior materials such as automobile interior materials, wallpaper and carpets, air filters and filter media It is extremely useful for filter materials such as

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. Here, in order to investigate the effect of the flame-retardant fiber of the present invention, the description will be given using the staple fiber which is one of the embodiments, but other forms can be easily made by referring to the examples. The present invention is not limited to staple fibers because they can be deployed. The terms and evaluation methods used in the examples and comparative examples are as follows.

(A) Melt Mass Flow Rate (MFR): Measured in accordance with Method B (automatic time measurement method) described in JIS K 7210 Thermoplastic Flow Test Method. High density polyethylene was measured under test condition D (temperature 190 ° C., load 2.16 kg), and polypropylene was measured under test condition M (temperature 230 ° C., load 2.16 kg).

(B) Melting point: Measured according to JIS K 7122 using a differential scanning calorimeter DSC Q10 (trade name) manufactured by TA Instruments.

(C) Fineness: The fineness was measured according to the positive fineness measurement method A described in JIS L 1015 chemical fiber staple measurement method.

(D) Tensile strength and elongation of fiber: Measured according to JIS L 1015 chemical fiber staple measuring method.

(E) Flame retardant performance evaluation:
* Afterflame time and carbonization area measurement Among the test pieces obtained in Examples 1 to 8 and Comparative Examples 1 to 8, using a non-woven fabric with a weight per unit area of 200 g / m ² , according to A-1 method of JIS L1901 Afterflame time (seconds) and carbonized area (cm ² ) were examined, and flame retardancy was evaluated based on the investigation. Smaller values for both afterflame time and carbonized area indicate better flame retardancy.
* Evaluation Based on the values obtained by the after-flame time / carbonized area measurement, the flame retardancy of each nonwoven fabric was evaluated in the following four stages. A: Very good. ○: Excellent. Δ: Although there is flame retardancy, it is not excellent. X: There is no flame retardancy or it is remarkably weak.

(F) Weather resistance evaluation:
* Nonwoven fabric strength measurement Among the test pieces obtained in Examples 1 to 8 and Comparative Examples 1 to 8, samples each having a basis weight of 60 g / m ² cut into a strip shape having a width of 2.5 cm and a length of 15 cm. It was. At room temperature, an autograph AGS500D (trade name) manufactured by Shimadzu Corporation was used and pulled at a speed of 100 mm / min until the sample broke. After measuring the tensile strength at break, it was converted to a basis weight of 60 g / m ^{2 according} to the following formula to obtain the nonwoven fabric strength (N / 2.5 cm).
Nonwoven fabric strength = tensile strength × 60 / weight of each nonwoven fabric sample * measurement of nonwoven fabric strength retention rate Among the test pieces obtained in Examples 1 to 8 and Comparative Examples 1 to 8, nonwoven fabrics each having a weight of 60 g / m ² The strength of each nonwoven fabric after irradiation for 40 hours, 80 hours, 120 hours, 160 hours, and 200 hours with an ultraviolet carbon arc lamp type light resistance tester described in JIS B 7751 is determined according to the strength evaluation of the nonwoven fabric. After the measurement, the percentage of the nonwoven fabric strength after irradiation with respect to the nonwoven fabric strength before irradiation was defined as the nonwoven fabric strength maintenance rate (%). The closer this value is to 100, the harder the deterioration of the non-woven fabric, that is, the better the weather resistance.
* Evaluation The weather resistance performance of each nonwoven fabric was evaluated in the following four stages based on the value obtained by the measurement of the nonwoven fabric strength retention rate. A: Very good. ○: Excellent. Δ: Although there is weather resistance, it is not excellent. X: There is no weather resistance performance or it is remarkably weak.

HDPE: high density polyethylene, melting point 130 ° C., MFR 15 (190 ° C.).
PP: polypropylene, melting point 165 ° C, MFR10 (230 ° C).
co-PP: ethylene-propylene-butene copolymer, melting point 135 ° C.,
MFR15 (230 ° C).
Flame retardant A: Cyclic phosphazene flame retardant, KEMIDANT 302S (trade name,
1,1,3,3,5,5-hexa (aryloxy) cyclotri
Phosphazene), manufactured by Chemipro Kasei Co., Ltd.
Flame retardant B: hindered amine flame retardant, FLAMESTAB NOR 116
(Trade name, compound represented by general formula (VI)), Ciba Special
Made by T Chemicals.
Flame retardant C: antimony trioxide.
Flame retardant D: Halogen flame retardant, GLC DE-83R (trade name), Greatray
Made by Ix Chemical Japan.
Additive E: Phosphorous antioxidant, IRGAFOS 168 (trade name), Ciba Su
Made by Specialty Chemicals.
Flame retardant F: Phosphate ester flame retardant, FP-500 (trade name), Asahi Denka Kogyo (
Made by Co., Ltd.

Example 1
A parallel type composite fiber was produced using a composite spinning apparatus having two extruders equipped with a parallel type composite spinning base.
A first component comprising PP as 98.4% by weight, flame retardant A as 1.5% by weight and flame retardant B as 0.1% by weight, and HDPE as 98.4% as the other component. %, Flame retardant A 1.5 wt% and flame retardant B 0.1 wt% of the second component are charged into the two extruders, each hopper, at a temperature of 250 ° C., The composite fiber was spun so that the volume ratio of the first component and the second component was a parallel fiber cross-sectional shape of 50/50, and this was wound up by a winder. In the winding step, an alkyl phosphate potassium salt was adhered as a surfactant to the surface of the spun composite fiber. Next, the composite fiber (undrawn yarn) wound up by a winder is drawn 4.5 times by a drawing machine under a temperature condition of 100 ° C., then passed through a stuffing box to give mechanical crimps, and then long Cut to 51 mm, a crimped 3.3 dtex fiber (staple fiber) was obtained. The resulting fiber was measured for tensile strength and elongation. The results are shown in Table 1.
Next, the obtained staple fiber is carded with a card machine to form a web, and the web is heat-treated with a hot air penetration type dryer at a temperature of 130 ° C. for a treatment time of 12 seconds so that the intersection of the composite fibers is heat-melted. A non-woven fabric (fiber shaped body) was obtained. Flame retardant performance evaluation and weather resistance performance evaluation were performed on the obtained nonwoven fabric. The results are shown in Table 1. In addition, the nonwoven fabric used for a flame retardance evaluation adjusts a fabric weight to 200 g / m < ² >, and the nonwoven fabric used for a weather resistance evaluation has adjusted the fabric weight to 60 g / m < ² >.

Examples 2-5
Except for the fiber composition shown in Table 1, each composite fiber and non-woven fabric was obtained by the production method according to Example 1, and the tensile strength and elongation rate of the fiber, the evaluation of flame retardancy and the weather resistance were evaluated. . The results are shown in Table 1.

Example 6
Conforms to Example 1 except that the fiber composition shown in Table 1 is used and the composite spinning device is used to have two extruders with a sheath-core-type composite spinneret and a sheath-core-type conjugate fiber is produced. By using the production method described above, each composite fiber and nonwoven fabric were obtained, and fiber tensile strength and elongation rate evaluation, flame retardant performance evaluation, and weather resistance performance evaluation were performed. The results are shown in Table 1.

Example 7
Other than having a fiber composition shown in Table 1 and having two extruders fitted with a sheath-core type composite spinneret, using a composite spinning device, spinning at 280 ° C. and drawing at 110 ° C. by 3.0 times Produced a sheath-core type composite fiber by the method according to Example 1. A nonwoven fabric was obtained by the production method according to Example 1 except that the heat treatment temperature of the web was 140 ° C., and fiber tensile strength and elongation rate evaluation, flame retardant performance evaluation, and weather resistance performance evaluation were performed. The results are shown in Table 1.

Example 8
A composite fiber and a non-woven fabric were produced by the manufacturing method according to Example 1 except that a parallel-type spinneret having a larger diameter than that of Example 1 was used in order to obtain the fiber composition shown in Table 1 and a fineness of 15.6 dtex. The fiber was evaluated for tensile strength and elongation, evaluation of flame retardancy, and evaluation of weather resistance. The results are shown in Table 1.

Comparative Examples 1-6
Except for the fiber composition shown in Table 2, each composite fiber and non-woven fabric was obtained by the production method according to Example 1, and the tensile strength and elongation rate evaluation, flame retardant performance evaluation, and weather resistance performance evaluation of the fiber were performed. . The results are shown in Table 2.

Comparative Example 7
Conforms to Example 1 except that the fiber composition shown in Table 2 is used and the composite spinning device is used to have two extruders fitted with a sheath-core type composite spinneret to produce sheath-core type composite fibers. By using the production method described above, each composite fiber and nonwoven fabric were obtained, and fiber tensile strength and elongation rate evaluation, flame retardant performance evaluation, and weather resistance performance evaluation were performed. The results are shown in Table 2.

Comparative Example 8
Except for spinning at 280 ° C and drawing at 3.0 times at 110 ° C using a compound spinning device to have two extruders with the fiber composition shown in Table 2 and fitted with a sheath-core type composite spinneret. Produced a sheath-core type composite fiber by the method according to Example 1. A nonwoven fabric was obtained by the production method according to Example 1 except that the heat treatment temperature of the web was 140 ° C., and fiber tensile strength and elongation rate evaluation, flame retardant performance evaluation, and weather resistance performance evaluation were performed. The results are shown in Table 2.

Comparative Example 9
Spinning of the composite fiber by the production method according to Example 1 except that a parallel type spinneret having a larger diameter than that of Example 1 was used in order to obtain the fiber composition shown in Table 2 and the fineness of 15.6 dtex. However, yarn breakage frequently occurred and fiber production was impossible.

From Table 1, it is clear that Examples 1-8 which are the flame-retardant fiber of this invention have the outstanding flame retardance performance and the weather resistance performance.
On the other hand, from Table 2, Comparative Example 1 in which no flame retardant is blended has extremely poor flame retardancy and weather resistance, and any of phosphazene derivatives and hindered amine derivatives that are essential components of the flame retardant fiber of the present invention. It is clear that Comparative Examples 2 and 3 in which the blending amount is outside the scope of the present invention does not have sufficient flame retardancy.
Moreover, it is clear from Table 2 that Comparative Examples 4 to 8 made of a flame retardant different from the flame retardant component constituting the flame retardant fiber of the present invention have a poor balance between flame retardant performance and weather resistance performance. In particular, Comparative Example 4 contains a flame retardant composition that is a combination of antimony trioxide and a halogen-based flame retardant, so that the flame retardant performance is excellent, but because the decomposition of the olefin resin is accelerated, the weather resistance is increased. The performance is extremely bad. In Comparative Examples 5 to 8, although the hindered amine derivative that is one of the essential components of the present invention is used, a phosphate ester-based flame retardant or phosphorus-based compound is used instead of the phosphazene derivative that is another essential component of the present invention. Since the antioxidant is combined with the hindered amine derivative, the weather resistance is excellent, but the flame retardancy is not sufficient.
Further, in Comparative Example 9, since the flame retardant component constituting the flame retardant fiber of the present invention is blended in a large amount beyond the scope of the present invention, the fiber is frequently cut during spinning, and operability is increased. It was impossible to make a fiber due to a significant drop.

  It can be used widely and suitably for various products such as automobile interior materials, interior materials, and filter materials.

Claims (5)

Flame retardant fiber made of thermoplastic resin containing flame retardant (excluding decabromodiphenyl oxide, bis (2,3-dibromopropyl) ether of tetrabromobisphenol A, ethylene bis-tetrabromophthalimide) The flame retardant is at least one phosphazene derivative selected from a cyclic phosphazene derivative represented by the following general formula (I) and a chain phosphazene derivative represented by the following general formula (II), represented by the following general formula (III): A hindered amine derivative containing a group, wherein the fiber contains 0.25 to 5.0% by weight of the phosphazene derivative and 0.025 to 3.0% by weight of the hindered amine derivative, and the total amount of the flame retardant component in the fiber amount is in the range of 1-6% by weight, flame retardant, wherein the fineness of the fiber is 0.01 to 50 dtex Fiber.

[Wherein, m is an integer of 3 to 10, and two Q's each independently represent a group selected from the group consisting of an alkoxy group, an aryloxy group and an amino group. ]

[Wherein, n is an integer of 3 to 10, and nine Qs each independently represent a group selected from the group consisting of an alkoxy group, an aryloxy group and an amino group. ]

[Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon group having 7 to 18 carbon atoms, or 7 to 15 carbon atoms. R ₂ , R ₃ , R ₄ and R ₅ independently represent a C 1-4 alkyl group, or R ₂ and R ₃ and / or R ₄ and R ₅ bonded penta R ₆ represents an alkoxyl group having 1 to 4 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an amino group having 1 to 18 carbon atoms, the following general formula (IV), and A represents an oxygen atom or N—R ₇ (wherein R ₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms). ]

[Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon group having 7 to 18 carbon atoms, or 7 to 15 carbon atoms. R ₂ , R ₃ , R ₄ and R ₅ independently represent a C 1-4 alkyl group, or R ₂ and R ₃ and / or R ₄ and R ₅ bonded penta Represents a methylene group, and A represents an oxygen atom or the following formula N—R ₇ (wherein R ₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms). ] The flame-retardant fiber according to claim 1, wherein the thermoplastic resin is a resin selected from a copolymer mainly composed of polyolefin and olefin. The flame-retardant fiber according to claim 1, wherein the fiber is a composite fiber. The fiber molded object using the fiber of any one of Claims 1-3 . Production of flame retardant fiber made of thermoplastic resin containing flame retardant (excluding decabromodiphenyl oxide, bis (2,3-dibromopropyl) ether of tetrabromobisphenol A, ethylene bis-tetrabromophthalimide) A flame retardant is at least one phosphazene derivative selected from a cyclic phosphazene derivative represented by the following general formula (I) and a chain phosphazene derivative represented by the following general formula (II), the following general formula (III) A hindered amine derivative containing a group represented by the formula: 0.25 to 5.0% by weight of the phosphazene derivative in the fiber, 0.025 to 3.0% by weight of the hindered amine derivative, and the total amount of the flame retardant component in the fiber. contain a flame retardant component so that the amount of additive is in the range of 1-6 wt%, fineness of 0.01 to 50 dtex fiber Method for producing a flame-retardant fiber characterized by the production of.

[Wherein, m is an integer of 3 to 10, and two Q's each independently represent a group selected from the group consisting of an alkoxy group, an aryloxy group and an amino group. ]

[Wherein, n is an integer of 3 to 10, and nine Qs each independently represent a group selected from the group consisting of an alkoxy group, an aryloxy group and an amino group. ]

[Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon group having 7 to 18 carbon atoms, or 7 to 15 carbon atoms. R ₂ , R ₃ , R ₄ and R ₅ independently represent a C 1-4 alkyl group, or R ₂ and R ₃ and / or R ₄ and R ₅ bonded penta R ₆ represents an alkoxyl group having 1 to 4 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an amino group having 1 to 18 carbon atoms, the following general formula (IV), and A represents an oxygen atom or N—R ₇ (wherein R ₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms). ]

[Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon group having 7 to 18 carbon atoms, or 7 to 15 carbon atoms. R ₂ , R ₃ , R ₄ and R ₅ independently represent a C 1-4 alkyl group, or R ₂ and R ₃ and / or R ₄ and R ₅ bonded penta Represents a methylene group, and A represents an oxygen atom or the following formula N—R ₇ (wherein R ₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms). ]