JP4423918B2 - Functional fiber and fiber molded body using the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a functional fiber having excellent flame retardancy and adhesiveness and a fiber molded body using the functional fiber.

  Pellet-like, film-like or stick-like hot melt adhesives are used to bond other materials, but when used to bond fabrics such as fiber webs and nonwoven fabrics to wood, the resulting adhesive is However, the air permeability and filterability inherent to the fabric cannot be utilized, and these physical properties are remarkably deteriorated, and the obtained adhesive has various problems such as high weight. is doing. Therefore, studies have been made to give adhesive performance to other materials to the fabric or the raw fiber itself without using a pellet-like, film-like or stick-like hot melt adhesive.

  A heat-adhesive composite long fiber having a modified polyolefin graft-polymerized with a specific vinyl monomer having good adhesiveness with other materials has been developed (for example, see Patent Document 1). This composite long fiber is excellent not only in the adhesiveness between the long fibers but also in the thermal adhesiveness with other materials, and is hardly reduced in air permeability and filterability, and is lightweight. However, since the obtained adhesive is a flammable substance in addition to having high air permeability, there is a problem that the flame retardance particularly emphasized when used for building materials is insufficient. Improvement in fuel performance has been desired. However, no means has been known for imparting flame retardancy to an adhesive or its raw fiber without hindering these thermal bonding performances.

  Conventionally known methods for flame-retarding fibers include organic halogen-based flame retardants typified by decabromodiphenyl oxide, flame retardants such as metal hydrates typified by aluminum hydroxide, and fibers such as thermoplastic fibers. And the like. Decabromodiphenyl oxide is used mainly for polyolefin fibers because it can be made highly flame-retardant by adding 5% by weight or more to the fibers in combination with antimony trioxide. However, the fiber to which the flame retardant is added has a problem that the flame retardant falls off from the surface during fiber production. Further, this fiber has various problems such as not only the possibility that dioxin analogues are generated during combustion, but also extremely poor light resistance (see, for example, Patent Document 2).

  On the other hand, aluminum hydroxide generates almost no harmful gas during combustion, and is added to thermoplastic fibers and used. By adding 33% by weight or more of aluminum hydroxide into the fiber, the fiber can be made flame-retardant. However, the obtained fiber has not only low flame retardant performance but also fiber strength is significantly lower than the fiber added with the organic halogen flame retardant, and the flame retardant is dropped from the surface during fiber production. (For example, refer to Patent Documents 3 to 5.) In order to further improve the flame retardant performance, it is expected that the flame retardant should be added at a higher level, making it difficult to produce the fiber itself.

  In recent years, a flame retardant using a cyclic phosphazene compound that is easy to handle, excellent in thermal stability, hydrolysis resistance and flame retardancy, and hardly generates harmful combustion gases has been developed (for example, Patent Document 6). reference.). However, although a molded product obtained by blending only this flame retardant has a high flame retardant effect, it has a problem that it is not suitable as an adhesive material because it has no adhesion to other materials.

  Thus, in these flame-retarding methods, the adhesiveness with other materials becomes insufficient, and a fiber having both flame retardancy and adhesiveness has not been obtained.

JP 2002-54069 A Japanese Patent Publication No. 60-7722 JP-A-5-295181 JP 61-296045 A Patent No. 2836152 JP 2001-192392 A

  Therefore, the problem of the present invention is that the modified polyolefin has an adhesive performance and is less likely to have a harmful effect on the human body and the environment at all stages of production, use and disposal, and is safer and less difficult. It is an object of the present invention to provide a functional fiber having excellent flame retardancy by containing a flame retardant and a fiber molded body using the functional fiber.

  The inventors of the present invention have made extensive studies in order to solve the above problems. As a result, it has been found that the above problems can be solved by producing a fiber containing a modified polyolefin and a nitrogen-containing phosphorus compound, and the present invention has been completed based on this finding.

式（１）において、ｍは３〜１０の整数であり、Ｑはアルコキシル、アリールオキシ及びアミノからなる群からそれぞれ独立して選ばれる基である。
式（２）において、ｎは３〜１０の整数であり、Ｑはアルコキシル、アリールオキシ及びアミノからなる群からそれぞれ独立して選ばれる基である。
［４］窒素含有リン化合物が、機能性繊維に対して０．２５〜５重量％の範囲で含有されていることを特徴とする前記［１］〜［３］のいずれか１項記載の機能性繊維。
［５］式（３）で示される基を有するヒンダードアミン誘導体が、機能性繊維に対して０．１〜３重量％の範囲で更に含有されていることを特徴とする前記［１］〜［４］のいずれか１項記載の機能性繊維。

式（３）において、Ｒ^１は、炭素数１〜１８のアルキル、炭素数５〜１２のシクロアルキル、炭素数７〜１２の二環式または三環式の炭化水素及び炭素数７〜１５のフェニルアルキルからなる群から選ばれる基であり、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、炭素数１〜４のアルキルからなる群からそれぞれ独立して選ばれる基、または、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、Ｒ^６は、炭素数１〜４のアルコキシル、炭素数６〜１２のアリールオキシ、炭素数１〜１８のアミノ、式（４）で示される基からなる群から選ばれる基であり、Ａは、酸素またはＮ−Ｒ^７を示し、Ｒ^７は水素、炭素数１〜１２の直鎖または分岐鎖のアルキルからなる群から選ばれる基である。
ここに、式（４）において、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＡは、式（３）と同様である。
［６］変性剤が、マレイン酸、アクリル酸、メタクリル酸及びそれらの無水物からなる群から選ばれる少なくとも１種であり、機能性繊維に対して該変性剤が０．００１〜２モル／ｋｇの範囲で含有されていることを特徴とする前記［１］項記載の機能性繊維。
［７］機能性繊維が、ポリオレフィン系繊維であることを特徴とする前記［１］〜［６］のいずれか１項記載の機能性繊維。
［８］機能性繊維が、ポリエステル系繊維であることを特徴とする前記［１］〜［６］のいずれか１項記載の機能性繊維。
［９］前記［１］〜［８］のいずれか１項記載の機能性繊維を用いた繊維成形体。 [1] Contains a modified polyolefin graft-polymerized with at least one vinyl monomer (hereinafter referred to as a modifier) selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and a nitrogen-containing phosphorus compound. Functional fiber.
[2] The functional fiber is a composite fiber composed of a second component containing a modified polyolefin and a first component having a melting point higher than that of the second component, and the second component is at least on the surface of the composite fiber. The functional fiber according to item [1], wherein a part of the functional fiber is formed continuously in the length direction, and the first component and / or the second component contains a nitrogen-containing phosphorus compound. .
[3] The nitrogen-containing phosphorus compound is at least one phosphazene derivative selected from the group consisting of a cyclic phosphazene derivative represented by the formula (1) and a chain phosphazene derivative represented by the formula (2). The functional fiber according to [1] or [2].

In Formula (1), m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of alkoxyl, aryloxy and amino.
In the formula (2), n is an integer of 3 to 10, and Q is a group independently selected from the group consisting of alkoxyl, aryloxy and amino.
[4] The function according to any one of [1] to [3], wherein the nitrogen-containing phosphorus compound is contained in a range of 0.25 to 5% by weight with respect to the functional fiber. Sex fibers.
[5] The above [1] to [4], wherein the hindered amine derivative having a group represented by the formula (3) is further contained in the range of 0.1 to 3% by weight with respect to the functional fiber. ] The functional fiber of any one of.

In the formula (3), R ¹ is alkyl having 1 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, bicyclic or tricyclic hydrocarbon having 7 to 12 carbon atoms, and 7 to 15 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ are groups independently selected from the group consisting of alkyls having 1 to 4 carbon atoms, or R ² and R ³ and / or pentamethylene in which R ⁴ and R ⁵ are bonded, R ⁶ is alkoxy having 1 to 4 carbon atoms, aryloxy having 6 to 12 carbon atoms, amino having 1 to 18 carbon atoms, represented by the formula (4) A represents oxygen or N—R ⁷ , and R ⁷ represents a group selected from the group consisting of hydrogen and linear or branched alkyl having 1 to 12 carbons. is there.
Here, in formula (4), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and A are the same as in formula (3).
[6] The modifier is at least one selected from the group consisting of maleic acid, acrylic acid, methacrylic acid and anhydrides thereof, and the modifier is 0.001 to 2 mol / kg with respect to the functional fiber. The functional fiber according to item [1], wherein the functional fiber is contained in the range of [1].
[7] The functional fiber according to any one of [1] to [6], wherein the functional fiber is a polyolefin-based fiber.
[8] The functional fiber according to any one of [1] to [6], wherein the functional fiber is a polyester fiber.
[9] A fiber molded body using the functional fiber according to any one of [1] to [8].

  The functional fiber of the present invention does not drop off the flame retardant, and can exhibit excellent flame retardant performance with a small amount of flame retardant used. Furthermore, since the functional fiber of the present invention has good physical strength in addition to good adhesion to other materials, it has flame resistance, adhesion and physical strength over a long period of time. Can be maintained. Furthermore, when incinerated or discarded, there is almost no adverse effect on the environment and human body. Moreover, since the fiber molded object which consists of a functional fiber of this invention has a flame retardance, it becomes possible to prevent an initial fire, when it uses as adhesives, such as building materials. Moreover, even if a fire breaks out, no harmful combustion gas is generated by the flame retardant, which is a problem with conventional halogen flame retardants. Moreover, the functional fiber of the present invention has good productivity because the flame retardant does not fall off and has high physical strength.

Hereinafter, the present invention will be described in detail.
The functional fiber of the present invention is a modified polyolefin (grafted with a vinyl monomer consisting of at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as a modifier) ( Hereinafter, this is simply referred to as “modified polyolefin”) and a nitrogen-containing phosphorus compound (hereinafter referred to as “flame retardant”). The modified polyolefin may be used alone, but it can also be used by mixing it with a thermoplastic resin and diluting it using a highly modified modified polyolefin. At this time, it is preferable that the thermoplastic resin to be diluted is the same type as the trunk polymer of the modified polyolefin.

In the present invention, the modifying agent used for the modified polyolefin is a vinyl monomer composed of at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, specifically, maleic acid, acrylic acid, It is at least one vinyl monomer selected from the group consisting of methacrylic acid and anhydrides thereof. In addition, you may make the modifier contain other vinyl monomers other than these. As the other vinyl monomer, a general-purpose monomer excellent in radical polymerizability can be used. Examples include styrenes such as styrene and α-methylstyrene, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, and acrylic acid esters similar to these. be able to.
The unsaturated carboxylic acid or unsaturated carboxylic acid anhydride grafted to the modified polyolefin is a component that directly contributes to adhesion to other materials. In addition, other vinyl monomers have the effect of uniformly dispersing the modified polyolefin, which is an adhesive component, in the thermoplastic resin and the effect of improving the affinity with other materials by imparting polarity to less polar polyolefins. Yes, indirectly contributes to adhesion to other materials. Other materials refer to natural materials such as pulp and metal materials such as aluminum foil.

The method of graft polymerization of these vinyl monomers to polyolefin can be performed by a known method. Examples thereof include a method in which polyolefin, a vinyl monomer, and a radical initiator are melt-kneaded and polymerized, a method in which polymerization is performed in a reaction vessel, and the like.
The amount of the modifier in the modified polyolefin can be calculated by measuring an infrared absorption spectrum. For example, when the modified polyolefin is a modified polyethylene obtained by graft-polymerizing polyethylene with maleic anhydride, the amount of the graft-modified modifier can be measured by the following operation.
The modified polyethylene is dissolved in boiling xylene, and the solution is poured into three times the amount of normal temperature acetone and cooled sufficiently. The filtrate of this liquid is further washed with acetone and vacuum dried to obtain a powdery modified polyethylene from which unreacted maleic anhydride has been removed. The powder amount of maleic anhydride can be calculated by forming this powder into a film and measuring the Fourier transform infrared absorption spectrum using the powder.
Polyolefin, polypropylene, or the like is preferable as the polyolefin serving as the main chain polymer of the modified polyolefin. As the polyethylene, a homopolymer of ethylene or a copolymer of ethylene and another α-olefin can be used. Specifically, low-density polyethylene having a density of 0.910~0.925g / cm ^3, linear low density polyethylene ^{0.926~0.940g / cm 3, 0.941~0.980g / cm} 3 General-purpose products such as high-density polyethylene can be used. These melting points are about 100-135 degreeC. Polyethylene having a lower density than these is commercially available and can be used. As the polypropylene, a homopolymer of propylene or a copolymer of propylene and an α-olefin such as 1-butene other than propylene can be used. These melting points are about 130-170 degreeC. Among these polymers, polyethylene is preferable in consideration of the melting point range and the ease of graft polymerization. The modified polyolefin used in the present invention is not only used alone, but also a mixture of two or more modified polyolefins, a mixture of a modified polyolefin main chain polymer and the same type polymer, or a modified polyolefin main chain polymer and a heterogeneous polymer. Can be used. When the modified polyolefin is used alone or as a mixture, the graft amount of the modifier in the functional fiber may be in the range of 0.001 to 2 mol / kg. If it is this range, a functional fiber can be produced with a well-known spinning apparatus, and adhesiveness with other materials can be exhibited.

As the form of the functional fiber used in the present invention, a single fiber, a composite fiber, or the like can be used. As the composite fiber, for example, a sheath core type composite fiber, an eccentric sheath core type composite fiber, a parallel type composite fiber, a split type composite fiber, a sea-island type composite fiber, etc. can be used, among which a sheath core type composite fiber, an eccentric sheath core type A composite fiber and a parallel composite fiber can be preferably used. In the case of a composite fiber, in order to exert thermal bonding performance, the composite fiber is composed of a second component containing a modified polyolefin and a first component having a melting point higher than that of the second component. A structure in which at least a part of the surface of the composite fiber is continuously formed in the length direction is preferable. Furthermore, when the modified polyolefin is used only for the second component of the composite fiber, the modified polyolefin can be included in the component constituting the fiber surface compared to a single fiber, so that the amount of the modified polyolefin can be used for adhesion. The function can be demonstrated. Further, the nitrogen-containing phosphorus compound only needs to be contained in the first component and / or the second component, but by adding only to the first component, the adhesiveness of the modified polyolefin is not inhibited, and the thermal adhesiveness is improved. It can be exhibited more effectively. Moreover, in order to increase the interlayer adhesive force between the first component and the second component and prevent peeling of both components, a modified polyolefin may be added to both components.
By using functional fibers in the form of composite fibers, the fiber web or fiber molded body is melted significantly due to the high heat generated by the hot air (heating) applied to the fiber molded body and the compressive force generated by embossing (pressing) during molding. Deformation can be prevented and the fiber shape can be maintained. This is desirable because the air permeability, elasticity, strength, etc. of the fiber web or fiber molded body can be maintained.

  As the thermoplastic resin used in the present invention, not only crystalline polymers such as polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, and polyamides such as nylon, but also these amorphous polymers can be used. When the functional fiber of the present invention is a composite fiber, the emphasis is placed on spinnability, chemical resistance, melting point, and the like. As a first component, crystalline propylene homopolymer or propylene and ethylene, 1-butene A crystalline propylene copolymer that is a copolymer with an α-olefin such as polyethylene terephthalate is preferable, and polyethylene terephthalate can be preferably used as the first component in view of strength, heat resistance, and the like. As the second component, polyethylene can be preferably used in consideration of the adhesiveness of the modified polyolefin. In addition, what is necessary is just to select the combination of a 1st component and a 2nd component according to an added value or required performance.

  The nitrogen-containing phosphorus compound used in the present invention can be used as long as it contains a phosphorus atom and a nitrogen atom in the molecule, and can exhibit a flame-retardant effect. Examples of the nitrogen-containing phosphorus compound include ammonium phosphate, melamine phosphate, ammonium polyphosphate, melamine polyphosphate, guanidine phosphate, phosphazene derivatives, and coating treatments thereof. Of these, phosphazene derivatives are particularly preferable.

式（１）において、ｍは３〜１０の整数であり、Ｑはアルコキシル、アリールオキシ及びアミノからなる群からそれぞれ独立して選ばれる基であり、式（２）において、ｎは３〜１０の整数であり、Ｑはアルコキシル、アリールオキシ及びアミノからなる群からそれぞれ独立して選ばれる基である。式（１）及び式（２）で示されるホスファゼン誘導体は、前記定義した範囲内であれば、特に限定されない。
前記アルコキシルは、メトキシ、エトキシ、ｎ−プロポキシ、ｉｓｏ−プロポキシ、ｎ−ブトキシ、ｉｓｏ−ブトキシ等の基を挙げることができ、その炭素数は１〜８が好ましい。前記アリールオキシは、例えば、非置換または、メチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｔｅｒｔ−ブチル、ｔｅｒｔ−オクチル、メトキシ、エトキシ、２，３−ジメチル、２，４−ジメチル、２，５−ジメチル、２，６−ジメチル、３，５−ジメチル、フェニル等で置換されたフェニルオキシ基等を挙げることができる。更に前記アリールとして、ナフチル等を挙げることもできる。前記アミノは、アミノ、メチルアミノ、エチルアミノ等の直鎖または分岐鎖を有するモノアルキルアミノ、ジメチルアミノ、ジエチルアミノ等の直鎖または分岐鎖を有するジアルキルアミノ等を挙げることができる。
また、式（２）で示されるホスファゼン誘導体には、製造工程において未反応物として残るハロゲンを含有している場合があるが、本発明は有害なガスの発生が極端に少ない難燃剤を目的としているため、該ホスファゼン誘導体中の全ハロゲン含有量を０．０５重量％以下にすることが望ましい。 The phosphazene derivative used in the present invention is a cyclic phosphazene derivative represented by the formula (1) and a chain phosphazene derivative represented by the formula (2).

In the formula (1), m is an integer of 3 to 10, Q is a group independently selected from the group consisting of alkoxyl, aryloxy and amino, and in the formula (2), n is 3 to 10 An integer, Q is a group independently selected from the group consisting of alkoxyl, aryloxy and amino. The phosphazene derivative represented by formula (1) and formula (2) is not particularly limited as long as it is within the above defined range.
Examples of the alkoxyl include groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, and the number of carbon atoms is preferably 1-8. The aryloxy is, for example, unsubstituted or methyl, ethyl, n-propyl, iso-propyl, tert-butyl, tert-octyl, methoxy, ethoxy, 2,3-dimethyl, 2,4-dimethyl, 2,5 -Phenyloxy group substituted by dimethyl, 2,6-dimethyl, 3,5-dimethyl, phenyl, etc. can be mentioned. Furthermore, examples of the aryl include naphthyl. Examples of the amino include linear or branched monoalkylamino such as amino, methylamino and ethylamino, and linear or branched dialkylamino such as dimethylamino and diethylamino.
Further, the phosphazene derivative represented by the formula (2) may contain a halogen remaining as an unreacted substance in the production process, but the present invention aims at a flame retardant with extremely little generation of harmful gas. Therefore, it is desirable that the total halogen content in the phosphazene derivative is 0.05% by weight or less.

  Examples of the cyclic phosphazene derivative represented by the formula (1) used in 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, 1,1,3,3,5,5-hexa (M- Ryloxy) 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) cyclotriphos Phazene, 1,1,3,3,5,5-hexa (4-tert-octylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (2,3-dimethylphenoxy) cyclotri Phosphazene, 1,1,3,3,5,5-hexa (2,4-dimethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (2,5-dimethylphenoxy) cyclotri Phosphazene, 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 (phenoxy) cyclotriphosphazene, , 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) cyclotriphosphazene, 1,3,5 -Tris (methoxy) -1,3,5-tris (o-tolyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (p-anisyloxy) cyclotriphosphazene, , 3,5-tris (methoxy) -1,3,5-tris (m-anisyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (o-anisyloxy) cyclo Triphosphazene, 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) cyclotriphosphazene, 1,3,5- Lis (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) cyclotriphos Fazen, 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-butylphenoxy) 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-propoxy) -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) cyclotriphosphazene, 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-tetrakis (n-butoxy) cycloto Phosphazene, 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) cyclotriphosphazene, 1,1-diamino- 3,3,5,5-tetrakis (m-anisyloxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-teto Lakis (o-anisyloxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (4-phenylphenoxy) cyclotriphosphazene and the like can be used.

  Examples of the chain phosphazene derivative represented by the formula (2) used in 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) triphosphazene 1,1,3,3 , 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-octylphenoxy) 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) Ii) -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) -1,3,5-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) triphosphazene, 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, 1,3,5-tris (methoxy)- 1,3,5-tris (4-tert-octylphenoxy) triphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (4-tert-butylphenoxy) triphosphazene, , 3,5-Tris (n-propoxy) -1,3,5-tris (4-tert-octylphenoxy) triphosphazene, 1,3,5-tris (methoxy)- , 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, 1,1-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 1,1-diamino-3,3,5,5-tetrakis (o-anisyloxy) triphosphazene, 1,1-diamino-3,3,5,5-tetrakis (4-phenylphenoxy) triphosphazene, and the like.

  The phosphazene derivative used in the present invention is at least one selected from the group consisting of a cyclic phosphazene derivative represented by the formula (1) and a chain cyclic phosphazene derivative represented by the formula (2), and any one of these is selected. Although it may be used, it may be used as a mixture of two or more, but in the present invention, it is particularly desirable to use a cyclic phosphazene derivative.

If the nitrogen-containing phosphorus compound is simply adhered to the surface of the molded article containing the modified polyolefin, there is a possibility that problems such as peeling off due to post-processing, post-treatment and long-term use may occur. Therefore, in this invention, it mix | blends with a thermoplastic resin so that it may exist in a fiber, a nitrogen-containing phosphorus compound is shape-processed, and it utilizes as various molded objects.
The functional fiber of the present invention is a thermoplastic fiber containing a modified polyolefin and a nitrogen-containing phosphorus compound that is a flame retardant. The addition amount of the nitrogen-containing phosphorus compound is preferably in the range of 0.01 to 20% by weight and more preferably in the range of 0.25 to 5% by weight with respect to the weight of the functional fiber. When the functional fiber is a single fiber, the flame retardant is dispersed almost uniformly throughout the fiber. However, in the case of a composite fiber, the first component and / or the second component contains a nitrogen-containing phosphorus compound. Because it can be used, by adding a flame retardant to the first component that does not contribute to thermal adhesiveness, the modified polyolefin that expresses the adhesive function and the nitrogen-containing phosphorus compound that expresses the flame retardant function are different components This is preferable because each performance can be sufficiently exhibited without impairing the mutual performance of flame retardancy and adhesiveness.

式（３）において、Ｒ^１は、炭素数１〜１８のアルキル、炭素数５〜１２のシクロアルキル、炭素数７〜１２の二環式または三環式の炭化水素及び炭素数７〜１５のフェニルアルキルからなる群から選ばれる基であり、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、炭素数１〜４のアルキルからなる群からそれぞれ独立して選ばれる基、または、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、Ｒ^６は、炭素数１〜４のアルコキシル、炭素数６〜１２のアリールオキシ、炭素数１〜１８のアミノ、式（４）で示される基からなる群から選ばれる基であり、Ａは、酸素またはＮ−Ｒ^７である。
また、式（４）において、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＡは、式（３）と同様である。 As the flame retardant aid for the phosphazene derivative, a hindered amine derivative having a group represented by the formula (3) can be preferably used.

In the formula (3), R ¹ is alkyl having 1 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, bicyclic or tricyclic hydrocarbon having 7 to 12 carbon atoms, and 7 to 15 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ are groups independently selected from the group consisting of alkyls having 1 to 4 carbon atoms, or R ² and R ³ and / or pentamethylene in which R ⁴ and R ⁵ are bonded, R ⁶ is alkoxy having 1 to 4 carbon atoms, aryloxy having 6 to 12 carbon atoms, amino having 1 to 18 carbon atoms, represented by the formula (4) And A is oxygen or N—R ⁷ .
In the formula (4), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and A are the same as in the formula (3).

式（５）において、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、式（３）と同様であり、Ｒ^７は水素、炭素数１〜１２の直鎖または分岐鎖のアルキルからなる群から選ばれる基である。また、式（６）において、Ｔ^１〜Ｔ^４は、水素、式（５）で示される基からなる群からそれぞれ独立して選ばれる基である。
なお、ここで、Ｒ^１同士が架橋反応を起こすこともあるが、反応物が存在していてもなんら差し支えない。
式（６）において、Ｔ^１、Ｔ^２、Ｔ^３が、式（５）で示される基であること、または、Ｔ^１、Ｔ^２、Ｔ^４が、式（５）で示される基であることが望ましく、具体的には、Ｎ，Ｎ’，Ｎ”−トリス｛２，４−ビス[（１−シクロヘキシルオキシ−２，２，６，６−テトラメチルピペリジン−４−イル）ｎ−ブチルアミノ]−ｓｙｍ−トリアジン−６−イル｝−３，３’−エチレンジイミノジプロピルアミン、Ｎ，Ｎ’，Ｎ”−トリス｛２，４−ビス[（１−シクロヘキシルオキシ−２，２，６，６−テトラメチルピペリジン−４−イル）ｎ−ブチルアミノ]−ｓｙｍ−トリアジン−６−イル｝−３，３’−エチレンジイミノジプロピルアミン、Ｎ，Ｎ’，Ｎ”−トリス｛２，４−ビス[（１−オクチルオキシ−２，２，６，６−テトラメチルピペリジン−４−イル）ｎ−ブチルアミノ]−ｓｙｍ−トリアジン−６−イル｝−３，３’−エチレンジイミノジプロピルアミン、Ｎ，Ｎ’，Ｎ”−トリス｛２，４−ビス[（１−メトキシ−２，２，６，６−テトラメチルピペリジン−４−イル）ｎ−ブチルアミノ]−ｓｙｍ−トリアジン−６−イル｝−３，３’−エチレンジイミノジプロピルアミン等を例示することができる。
本発明に用いるヒンダードアミン誘導体は、前記ヒンダードアミン誘導体のいずれか１種を用いても、２種以上を混合して用いてもよい。ヒンダードアミン誘導体とホスファゼン誘導体とを同時に添加する場合、特定比率にて配合すると相乗効果により非常に優れた難燃性能を示す。その配合比率は、ヒンダードアミン誘導体／ホスファゼン誘導体が、０．００５〜３００の範囲であることが好ましく、０．０１〜４の範囲であることがより好ましい。 The hindered amine derivative used for the flame retardant aid of the present invention has a structure having a hindered amine part having weather resistance and a sym-triazine part having flame resistance. The hindered amine derivative having this structure has a good compatibility with the phosphazene derivative, and when used in combination, provides extremely excellent flame retardancy. Especially, the hindered amine derivative which has group shown by Formula (5) is preferable, and the hindered amine derivative shown by Formula (6) is still more preferable.

In the formula (5), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as those in the formula (3), and R ⁷ is hydrogen, a linear or branched alkyl having 1 to 12 carbon atoms. A group selected from the group consisting of In Formula (6), T ^{1 to} T ⁴ are groups independently selected from the group consisting of hydrogen and a group represented by Formula (5).
Here, R ¹ may cause a cross-linking reaction, but there is no problem even if a reaction product exists.
In Formula (6), T ¹ , T ² , and T ³ are groups represented by Formula (5), or T ¹ , T ² , and T ⁴ are groups represented by Formula (5). In particular, N, N ′, N ″ -tris {2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) n-butyl Amino] -sym-triazin-6-yl} -3,3′-ethylenediiminodipropylamine, 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-tetramethylpiperidi -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 Can do.
As the hindered amine derivative used in the present invention, any one of the hindered amine derivatives may be used, or two or more thereof may be mixed and used. When a hindered amine derivative and a phosphazene derivative are added at the same time, if they are blended at a specific ratio, they exhibit excellent flame retardancy due to a synergistic effect. The blending ratio of the hindered amine derivative / phosphazene derivative is preferably in the range of 0.005 to 300, and more preferably in the range of 0.01 to 4.

  In the functional 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, antioxidants, light stabilizers, UV absorbers, neutralizers, nucleating agents, epoxy stabilizers, lubricants, antibacterial agents, antistatic agents, pigments, plasticizers, metal deactivators, hydrophilic agents, etc. it can. Moreover, you may mix | blend various fillers, electroconductive powder, another flame retardant, a flame retardant adjuvant, etc. as needed.

  The functional fiber of the present invention can be used after being processed into a short fiber or a long fiber according to the application. The functional fiber of the present invention can be obtained as a short fiber by performing crimping treatment as necessary after cutting and drawing and cutting into a predetermined length. Further, the functional fiber of the present invention can be obtained in the state of a long fiber tow by not cutting after spinning and drawing. When the functional fiber of the present invention is cut and used, the fiber length is not particularly limited and can be appropriately selected depending on the application. However, the tensile strength sufficient for a fiber molded body obtained by heat-sealing fibers together. Is preferably 2 mm or more. When the fiber is used in the card method, although it depends on the fineness, a highly uniform web can be obtained if the fiber length is generally 20 to 76 mm. Moreover, when using for a papermaking method or an airlaid method, the fiber length of 2 mm-20 mm is generally preferable. Furthermore, these fibers may be used alone to form a fiber molded body, but if it is within the range that does not significantly impair the effects of the present invention, the fibers and other fibers as necessary are blended. It may be mixed. Further, fibers formed with different resin configurations and other fibers may be mixed or mixed.

  The fiber molded body of the present invention can be produced by a known method. For example, after the fibers of the present invention are cut to a predetermined length, a fiber molded body (web) is obtained by a dry method such as a card method or a wet method such as a papermaking method, and is heated by a heating roll or ultrasonic waves or melted by heated air. A method of forming a non-woven fabric by entanglement, fiber entanglement with a high-pressure water stream or a needle, etc., a method of laminating the fibers cut to a predetermined length by an airlaid method, and heat-treating with a heating roll or heated air to make a non-woven fabric, the present invention After cutting the functional fiber into a predetermined length, a sliver is formed by a card method, and this is heat-treated into a fiber molded body, and the functional fiber of the present invention is used as a spun yarn, a continuous yarn, etc. Examples thereof include a method of forming a knitted fabric by processing. In particular, since the functional fiber of the present invention mainly contains a flame retardant inside the fiber, compared to a fiber having a flame retardant adhered to the surface by a method such as dipping in a solution, the card method or high-pressure water flow treatment is used. The flame retardant that falls off the fiber can be extremely suppressed. In addition, a method of obtaining a fiber molded body by a spunbond method or a melt blow method, a method of obtaining a fiber molded body by heat treatment with a superheated roll or heated air without cutting the tow of long fibers, and the like can be used. The functional fiber of the present invention may be a fiber molded body such as a woven fabric, a knitted fabric, a nonwoven fabric, and a filter using only the fiber, and may be other as necessary as long as the effect of the present invention is not significantly impaired. These fibers and the like may be blended, blended, or blended to form a fiber molded body.

  Specific examples of the other fibers include polyamide {for example, nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, nylon 612 and other aliphatic polyamides, nylon MXD6 (MXD: metaxylylene diamine), etc. Semi-aromatic polyamides, copolymers of aliphatic polyamides and semi-aromatic polyamides, and mixtures thereof}, wholly aromatic polyamides (for example, para-aramid and meta-aramid), polyamide-imide, polyimide, polyester (for example, Polyethylene terephthalate, polybutylene terephthalate), synthetic fibers such as wholly aromatic polyester, polyolefin, acrylic, natural fibers such as cotton, wool, hemp, etc., regenerated fibers such as rayon, cupra, acetate, semi-synthetic fibers, polylactic acid fibers, poly Butylene succinate fiber Biodegradable fiber, pulp, glass fibers, other available carbon fibers or the like, the fiber according to these other fibers can be utilized those flame-retarded.

  The cross-sectional shape of the functional fiber used in the present invention is not limited to a circular shape, and an elliptical shape, a boomerang shape, a cross-shaped shape such as a cross shape, etc. can be used. It may be formed. In the case of the composite fiber, composite forms such as a parallel type, a multi-partition type, a concentric sheath core type, an eccentric sheath core type, and the like can be given, and a fiber molded body may be formed by combining functional fibers of each composite form. In the case of a composite fiber composed of two components, the volume ratio of the first component to the second component (corresponding to the ratio of the cross-sectional area when the fiber cross-sectional area is adopted for the measurement) is usually the first component. : The volume ratio of the second component is preferably 10:90 to 90:10, more preferably 30:70 to 70:30. When the volume ratio is in the range of 10:90 to 90:10, the adhesiveness, flame retardancy, and spinnability are improved. In particular, the volume ratio in the range of 30:70 to 70:30 is preferable because the core component can firmly maintain the fiber shape when heat treatment or the like is performed. The effects of the present invention can be achieved even if the composite form is not only the above two-component form but also a three-component form or more.

  What is necessary is just to select the fineness of the functional fiber which comprises the fiber molded object used for this invention suitably according to a use, and about 0.01-100 dtex is normally used. In consideration of adhesiveness and productivity, 0.01 to 50 dtex is preferable, and 0.1 to 20 dtex is more preferable. In civil engineering material use, agricultural material use, and the like, fibers with a finer fineness may be required, and an optimum fineness may be selected and adjusted depending on the application.

When the fiber molded body of the present invention is a non-woven fabric, the basis weight may be appropriately selected according to the type and use of the resin used as a raw material, but considering air permeability and productivity, 5 to 200 g / m ² 5 to 50 g / m ² is particularly preferable.

  In order to impart functions such as antistatic property, fiber opening property, and smoothness to the functional fiber or fiber molded body of the present invention, a surfactant can be attached to the surface. As a method for attaching the surfactant to them, a roller method, a dipping method, a pad dry 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. If necessary, the surfactant may be attached to the surface after processing into a fiber molded body.

  Hereinafter, the case where a general yarn-making method is used about the manufacturing method of the functional fiber and fiber molded object of this invention is demonstrated. The raw material resin is, for example, a crystalline polypropylene having a higher melting point than the second component, using a resin composition containing a modified polyolefin obtained by graft-polymerizing maleic anhydride and linear low-density polyethylene as the second component. A resin composition containing a cyclic phosphazene derivative or a cyclic phosphazene derivative and a hindered amine derivative is used as the first component. These resins are spun by a general hot melt spinning machine equipped with a sheath-core type composite spinneret. At this time, the semi-molten resin to be discharged is cooled and solidified by blowing air from the quenching device just below the die, and an unstretched fiber (hereinafter referred to as unstretched yarn) is manufactured. In this step, a surface treatment agent may be attached as necessary. In consideration of the case of stretching, the discharge amount of the melted resin and the take-up speed of the undrawn yarn are arbitrarily set to obtain an undrawn yarn having a fiber diameter of about 1.1 to 5 times the target fineness. . The obtained undrawn yarn can be made into a drawn yarn by drawing with a general drawing machine. The drawn yarn is a fiber that has been subjected to drawing processing but not crimped. Usually, in the drawing roll heated to 30 to 120 ° C., the drawing treatment is performed so that the speed ratio between the inlet side of the undrawn yarn and the outlet side roll is in the range of 1: 1.1 to 1: 5. . If necessary, a surface treatment agent such as a surfactant is attached to the drawn yarn obtained by the drawing treatment with a touch roll or spray, and then crimped by a box-type crimping machine. The drawn yarn to which crimps have been imparted is dried at a temperature of 50 to 120 ° C. with a dryer, cut to a desired fiber length with a push cutter and used according to the intended use. In this way, functional short fibers can be obtained. Further, the functional fiber is made into a web by a generally known carding method, air laid method, paper making method or the like, and the obtained web is generally known as a point bond method, a hot air heating method, a high pressure water flow method. The molded body may be formed by a processing method such as a needle punch method or an ultrasonic bonding method, or may be further processed in combination. In addition, the drawn yarn may be processed from the state of the tow which is a long fiber without being cut short, and the tow can be processed into a rod-shaped formed body by heat treatment, and processed into a nonwoven fabric by a tow opening method. be able to.

  Hereinafter, the method for producing the functional fiber and the fiber molded body of the present invention will be described using the spunbond method as an example. As the raw material resin, for example, a resin composition containing a linear low density polyethylene graft-polymerized with maleic anhydride is used as a second component, and a cyclic phosphazene derivative or a cyclic phosphazene derivative is derived from crystalline polypropylene having a melting point higher than that of the second component. And a resin composition containing a hindered amine derivative was used as the first component. A general-purpose composite spunbond spinning machine having two extruders is used, each resin is put into each extruder, and the molten resin is discharged as long fibers from a composite spinneret kept at a high temperature. The discharged long fiber group is introduced into the air soccer and pulled and stretched, and then the long fiber group is discharged from the air soccer and collected on the conveyor. At this time, there are a method of collecting the long fiber group directly on the suction conveyor as a long fiber web, and a method of opening the fiber before collecting on the conveyor and then collecting. Examples of the method for opening the fiber include a method in which the long fiber group is passed between a pair of vibrating blades (flaps) in the middle of discharging the long fiber group, a method in which the long fiber group collides with a reflector, etc., corona charging Examples thereof include a method of charging a long fiber group by a method. The collected long fiber web is conveyed by a suction conveyor and subjected to heat treatment. As the heat treatment, for example, in a point bond processing machine constituted by a heated uneven roll and a smooth roll, a web is introduced between the pressed rolls, and in an area corresponding to the convex portion of the uneven roll, This is performed by melting or softening the second component and thermally fusing the long fibers (point bond method). Thereby, a fiber molded body is obtained. At this time, the basis weight of the fiber molded body can be adjusted by setting the spinning discharge speed (discharge amount per hour), the moving speed of the suction conveyor, and the like. The non-woven fabric processing is not limited to the point bond method, and may be performed by a hot air heating method, a high-pressure water flow method, a needle punch method, an ultrasonic bonding method, or the like, or a combination thereof.

  Hereinafter, the method for producing the functional fiber and the fiber molded body used in the present invention will be described by taking the melt blow method as an example. Using a general-purpose composite melt blow spinning machine with two extruders, the resin used as the first component and the second component is put into each extruder as in the spunbond method, and discharged at a high temperature. By discharging high-speed, high-speed hot air from both sides of the discharge hole, the fine fiber group is made into a long-fiber web on a suction conveyor or suction drum. Collect. Since the web obtained by the melt-blowing method is heat-sealed, it has a non-woven fabric strength at a level that causes no problem in handling the web. Therefore, it can be used as it is without being thermally processed. However, depending on the application, processing such as a point bond method may be further performed in the same manner as the spun bond method.

  Among these production methods, the spunbond method is particularly characterized in that a fiber molded article excellent in mechanical properties such as tensile strength can be easily obtained. Moreover, in the spunbond method and the melt blow method, long fibers obtained by melt spinning can be opened and collected as they are to be processed into a fiber molded body, so that the fiber molded body can be manufactured with excellent productivity and at low cost. Therefore, it is preferable. Furthermore, by using a spunbond method or a melt blow method, a fiber molded body can be produced without using a surface treating agent that may reduce the adhesive force when the fiber molded body is bonded to another material. For this reason, it has the characteristic that it is especially excellent in the adhesive force with another raw material compared with the fiber molded object obtained by the general spinning method which requires a surface treatment.

Moreover, the functional fiber molded object laminated body which laminated | stacked the fiber molded object obtained by the spunbond method and the fiber molded object obtained by the melt blow method, and joined with the point bond processing machine etc. can be utilized for this invention. For example, SM (spunbond nonwoven fabric / meltblown nonwoven fabric), SMS (spunbond nonwoven fabric / meltblown nonwoven fabric / spunbond nonwoven fabric), SMMS (spunbond nonwoven fabric / meltblown nonwoven fabric / meltblown nonwoven fabric / spunbond) Nonwoven fabric laminate) and the like. Furthermore, a laminate in which a fiber molded body obtained by a spunbond method or a melt blow method and a web by a functional fiber carding method, an airlaid method, a papermaking method, or the like can be used.
When the fiber molded body is a laminate, all of the laminated fiber molded bodies may contain the modifier and / or nitrogen-containing phosphorus compound used in the present invention, but the modifier and / or nitrogen-containing phosphorus compound. It may be a laminate of a fiber molded body using a part of. In this case, 0.001 to 2 mol / kg of the modifying agent and 0.1 to 10% by weight of the nitrogen-containing phosphorus compound may be contained in the functional fiber constituting the fiber molded body.
The fiber molded body or functional fiber molded body used in the present invention can be subjected to secondary processing at the time of heat treatment or after heat treatment, if necessary, so that a molded body having an arbitrary shape can be obtained. For example, long fibers can be bundled at the web stage, heat treated, etc., and bonded at the fiber intersections to form rods and other shaped products. It is possible to obtain molded bodies having various shapes by filling the container and heat-treating and bonding the fiber intersections.

  Since the functional fiber or fiber molded body of the present invention has excellent adhesion performance and flame retardancy, it can be used for aircraft, marine and automobile materials, interior materials thereof, wallpaper, carpet and other interior materials, air filters, etc. It is extremely useful as a filter material such as a filter material and an adhesive material such as clothing.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. The terms and evaluation methods used in each example and each comparative example are as follows.

(Melt flow rate)
The melt flow rate value of the thermoplastic resin was measured in accordance with Operation B method (automatic time measurement method) described in JIS K 7210 Thermoplastic Flow Test Method. Polyethylene was measured under test condition 4 (temperature 190 ° C., load 21.18 N). Polypropylene was measured under test condition 14 (temperature 230 ° C., load 21.18 N).

(Melting point)
The melting point of the thermoplastic resin was measured according to JIS K7122, using a differential scanning calorimeter DSC Q10 (trade name) manufactured by TA Instruments.

(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 6, using a non-woven fabric of 200 g / m ² per unit area, according to JIS L 1901 A-1 method. 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 inferior.

(Adhesion evaluation)
* Adhesiveness with aluminum foil The functional fibers obtained in Examples 1 to 8 and Comparative Examples 1 to 6 were molded so as to be nonwoven fabrics (fiber molded bodies) having a basis weight of 30 g / m ² . Next, the nonwoven fabric was cut into 5 cm (width) × 10 cm (length), and the sample (nonwoven fabric) was cut from both sides with an adherend (aluminum foil) having a thickness of 20 μm, similarly cut into 5 cm (width) × 10 cm (length). They are sandwiched and overlapped so that the four corners are aligned, and a heat seal elongated in the short side direction, that is, the width direction of the overlapped sample is applied. As a heat seal processing machine, using “Heat Seal Tester TP-701” (trade name) manufactured by Tester Sangyo Co., Ltd., processing is performed so that the part of 5 cm (width) × 1 cm (length) is heat sealed. (Refer to the explanatory diagram showing the configuration of the peel strength test sample in FIG. 1). The heat sealing conditions are a temperature of 140 ° C. (both up and down), a pressurization time of 3 seconds, and a pressure of 0.3 MPa.
Open the adhesive sample for peel strength obtained by this method from the short side of the other side different from the heat-sealed side, and adjust each edge of the non-adhered sample so that the distance between the chucks is 10 cm. The tensilon tensile tester “ROM-100” (trade name) manufactured by Orientec Co., Ltd. was fixed so that no slack occurred between the chucks. The peel strength was measured at a pulling speed of 100 mm / min (see the explanatory diagram showing the method of performing the peel strength test in FIG. 2). The calculation method of peel strength was based on JIS L 1086-1983.

(Environmental consideration)
Whether the functional fibers obtained in Examples 1 to 8 and Comparative Examples 1 to 6 may contain harmful substances that adversely affect the human body and the environment during combustion or disposal in two stages. evaluated. In addition, about the time of combustion, when functional fiber was burned, it was estimated whether a halogen compound or a dioxin analog was contained in combustion gas or residue. At the time of disposal, it was judged whether or not harmful substances were included from the materials added to the functional fibers.
A: Contains no substances that adversely affect the human body or the environment during combustion or disposal.
×: There is a possibility that a substance that adversely affects the human body or the environment during combustion or disposal is included.

(Raw resin)
PP: crystalline polypropylene (propylene homopolymer, MFR36, melting point 161 ° C.)
HDPE: high density polyethylene (ethylene homopolymer, Mw / Mn = 4.2, MI30, melting point 132 ° C., density 0.955 g / cm ³ )
LLDPE: linear low density polyethylene (ethylene-butene-1 copolymer, Mw / Mn = 3.5, MI20, melting point 122 ° C., density 0.920 g / cm ³ )
Modified PP (modified polypropylene): a copolymer obtained by graft polymerization of maleic anhydride using a polypropylene homopolymer as a main chain polymer (maleic anhydride content 0.05 mol / kg, MFR 3.0, melting point 165 ° C., density 0.910 g / cm ³ )
Modified PE (modified polyethylene): High-density polyethylene (ethylene homopolymer, Mw / Mn = 4.0, MI 2.0, melting point 132 ° C., density 0.960 g / cm ³ ) as a main chain polymer, graft polymerization of maleic anhydride Copolymer (maleic anhydride content 0.2 mol / Kg)
PET: Polyethylene terephthalate (IV 0.63, melting point 255 ° C.)
Flame retardant A: Cyclic phosphazene derivative type flame retardant “KEMIDANT 302S” (trade name) manufactured by Chemipro Kasei Co., Ltd.
Flame retardant B: Hindered amine derivative type flame retardant “FLAMESTAB NOR 116” (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd.
Flame retardant C: Antimony trioxide flame retardant D: Halogen flame retardant “GLC DE-83R” (trade name) manufactured by Great Lakes Chemical Japan
Flame retardant E: Inorganic flame retardant (magnesium hydroxide)
"Kisuma-5A" (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.

  Among the functional fibers constituting the fiber molded bodies of Examples and Comparative Examples, long fibers are produced by a known spunbond method or melt blow method, and short fibers are produced by a known composite fiber spinning method. It was produced by stretching and cutting to an arbitrary length.

A method for producing a fiber molded body using a spunbond method.
Fiber shaped bodies were produced using a composite spunbond spinning machine with two extruders. The raw material thermoplastic resin (the aforementioned thermoplastic resin or resin composition) is introduced into each extruder using a sheath core type or parallel type composite spinneret, the spinning temperature of the core component is 260 ° C., and the sheath component The spinning temperature was set to 260 ° C., the volume ratio of the first component to the second component was set to 50:50, and the molten resin was discharged as long fibers from the spinneret. The discharged long fiber group was pulled and stretched by air soccer, discharged on a suction conveyor, and collected as a long fiber web. The air soccer traction speed was adjusted so that the fineness at this time was 3 dtex / f. The obtained long fiber web was conveyed by a conveyor and pressed between rolls of a point bond processing machine constituted by a heated uneven roll and a smooth roll. Thereby, the 2nd component fuse | melted or softened in the area corresponding to the convex part of an uneven | corrugated roll, and the fiber molded object by which the long fibers were heat-sealed was obtained. Suction conveyor moving speed and point bond processing according to the type of fiber so that the basis weight of the fiber molded body is 30 g / m ² for evaluating adhesiveness with aluminum foil and 200 g / m ² for evaluating flame retardancy. The roll speed of the machine was adjusted.

A method for producing a fiber molded body using a melt blow method.
A melt-blown sheath core type or parallel type composite spinneret having a hole diameter of 0.3 mm and a number of holes of 501 in a row was used, the spinning temperature of the first component was 290 ° C., and the spinning temperature of the second component was 260. The long fiber web was obtained by setting the volume ratio of the first component and the second component to 50:50, and blowing the molten resin extruded from the spinneret onto the net conveyor with pressurized air at 380 ° C. . The obtained long fiber web was heated to 145 ° C. with a far-infrared heater while being transferred by a net conveyor, and a fiber molded body in which the second component was melted or softened in this area and the long fibers were heat-sealed. Obtained. The net conveyor moving speed was adjusted according to the type of fiber so that the basis weight of the fiber molded body was 30 g / m ² for evaluating adhesiveness with aluminum foil and 200 g / m ² for evaluating flame retardancy.

A method for producing a fiber molded body using a general composite fiber spinning method.
In a composite spinning apparatus having a sheath core type or parallel type composite spinneret with a hole diameter of 0.6 mm, the spinning temperature of the first component is 260 ° C., the spinning temperature of the second component is 260 ° C., and the first component and The volume ratio of the second component was set to 50:50, and spinning was performed at a take-up speed of 1000 m / min to obtain a concentric sheath-core type composite undrawn yarn having a single yarn fineness of 4.0 dtex / f. Next, the composite undrawn yarn is drawn under the conditions of a draw ratio of 2.4 times and a drawing temperature of 95 ° C., imparted with mechanical crimping, dried at 80 ° C., and then cut with a cutter into the fiber length according to the application. The short fiber was manufactured. The fiber for the miniature card machine was cut to 25 mm, and the fiber for the airlaid machine was cut to 5 mm. The obtained short fiber was made into a web with a miniature card machine or an airlaid machine, and then subjected to a heat treatment at 145 ° C. for 5 minutes in a hot air circulation dryer to obtain a fiber molded body. In addition, it adjusted according to the kind of fiber so that the fabric weight may be 30g / m < ² > for the adhesive evaluation with an aluminum foil, and 200g / m < ² > for a flame-retardant evaluation.

Example 1
Parallel composite fibers were produced by a general composite fiber spinning method using a composite spinning apparatus having two extruders equipped with a parallel composite spinneret.
One component comprising 88.4 wt% PP, 1.5 wt% flame retardant A, 0.1 wt% flame retardant B, and 10 wt% modified PP resin as one component, and the other side A second component comprising 88.4% by weight of HDPE, 1.5% by weight of flame retardant A, 0.1% by weight of flame retardant B and 10% by weight of modified PE resin, The composite fiber is spun into each hopper and spun at a temperature of 260 ° C. so that the volume ratio of the first component to the second component is a 50:50 parallel fiber cross-sectional shape. This was wound up. 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 A 3.3 dtex fiber (staple fiber) having been crimped to 51 mm was produced.
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. About the obtained nonwoven fabric, flame-retardant performance evaluation and adhesive evaluation with aluminum foil were implemented. The results are shown in Table 1. In addition, the nonwoven fabric used for a flame retardance evaluation adjusted the fabric weight to 200 g / m < ² >, and the nonwoven fabric used for an adhesive evaluation with aluminum foil adjusted the fabric weight to 30 g / m < ² >.

Example 2
Except for the fiber composition shown in Table 1, each composite fiber and non-woven fabric was produced by the production method according to Example 1, and flame retardant performance evaluation and adhesive evaluation with aluminum foil were performed using these. did. The results are shown in Table 1.

Example 3
Except for the fiber composition shown in Table 1, each composite fiber and non-woven fabric was produced by the production method according to Example 1, and flame retardant performance evaluation and adhesive evaluation with aluminum foil were performed using these. did. The results are shown in Table 1.

Example 4
Using a composite spinning apparatus having two extruders equipped with a sheath-core type composite spinning die, sheath-core type composite fibers were produced using a spunbond method.
A first component consisting of 98.0 wt% PP as the core component and 2.0 wt% flame retardant A, and a second component consisting of 90.0 wt% LLDPE and 10 wt% modified PE resin as the sheath component Are fed into each of the two extruders and each hopper, and at a temperature of 260 ° C., the volume ratio of the first component to the second component is 50:50, and the fiber cross-sectional shape is a concentric sheath core type fiber. The composite fiber was spun as follows. The discharged long fiber group was pulled and stretched by air soccer, discharged on a suction conveyor, and collected as a long fiber web. The air soccer traction speed was adjusted so that the fineness at this time was 3 dtex / f. The obtained long fiber web was conveyed by a conveyor and pressed between rolls of a point bond processing machine constituted by a heated uneven roll and a smooth roll. Thereby, in the area corresponding to the convex part of the concavo-convex roll, the second component was melted or softened to obtain a nonwoven fabric (fiber molded body) in which the long fibers were heat-sealed. In addition, the nonwoven fabric used for a flame retardance evaluation adjusted the fabric weight to 200 g / m < ² >, and the nonwoven fabric used for an adhesive evaluation with aluminum foil adjusted the fabric weight to 30 g / m < ² >.

Example 5
Except for the fiber composition shown in Table 1, each composite fiber and non-woven fabric was manufactured by the manufacturing method according to Example 4, and the flame resistance performance evaluation and the adhesive evaluation with the aluminum foil were performed using these. did. The results are shown in Table 1.

Example 6
Except for the fiber composition shown in Table 1, each composite fiber and non-woven fabric was manufactured by the manufacturing method according to Example 4, and the flame resistance performance evaluation and the adhesive evaluation with the aluminum foil were performed using these. did. The results are shown in Table 1.

Example 7
Using a composite spinning apparatus having two extruders equipped with a sheath-core type composite spinneret, a sheath-core type composite fiber was produced using a melt blow method. First component comprising 98.0 wt% PP as core component, 1.5 wt% flame retardant A and 0.5 wt% flame retardant B, and 88.0 wt% LLDPE as sheath component, flame retardant A second component consisting of 1.5% by weight of A, 0.5% by weight of flame retardant B, and 10% by weight of modified PE resin is introduced into the two extruders and the respective hoppers, and the core component The spinning temperature of 290 ° C. and the sheath component spinning temperature of 260 ° C., the volume ratio of the first component to the second component set to 50:50, and the molten resin extruded from the spinneret was pressurized at 380 ° C. A long fiber web was obtained by blowing on a net conveyor with air. The obtained long fiber web was heated to 145 ° C. with a far infrared heater while being transferred by a net conveyor, and the second component was melted or softened in this area and the non-woven fabric (fiber forming) Body). In addition, the nonwoven fabric used for flame-retardant evaluation adjusted the fabric weight to 200 g / m < ² >, and the nonwoven fabric used for adhesive evaluation with an aluminum foil adjusted the fabric weight to 30 g / m < ² >.

Example 8
Other than having the fiber composition shown in Table 1 and having two extruders fitted with a sheath-core type composite spinneret, spinning at 300 ° C. using a composite spinning apparatus and stretching at 3.0 times at 110 ° C. Produced a sheath-core type composite fiber by the method according to Example 1. Except that the heat treatment temperature of the web was 140 ° C., the non-woven fabric was evaluated for flame retardancy and adhesion performance with aluminum foil by the production method according to Example 1. The results are shown in Table 1.

Comparative Examples 1-3
Except for the fiber composition shown in Table 2, each composite fiber and non-woven fabric was produced by the production method according to Example 1, and flame retardant performance evaluation and adhesion performance evaluation with aluminum foil were performed using these. did. The results are shown in Table 2.

Comparative Examples 4-6
Except for the fiber composition shown in Table 2, each composite fiber and non-woven fabric was manufactured by the manufacturing method according to Example 4, and flame retardant performance evaluation and adhesive performance evaluation with aluminum foil were performed using these. did. The results are shown in Table 2.

Reference Examples 1-2
Except for the fiber composition shown in Table 2, an attempt was made to produce a composite fiber by the production method according to Example 4, but since the odor around the spinning tower was severe and yarn breakage occurred frequently, the fiber production was It was impossible.

From Table 1, it is clear that the fibers of Examples 1 to 8 using the flame retardant composition of the present invention have excellent flame retardant performance and adhesive performance with aluminum foil.
On the other hand, from Table 2, Comparative Example 1 in which both the flame retardant and the modified polyolefin were not added had poor flame retardancy and adhesion performance to the aluminum foil.
In Comparative Example 2 in which the phosphazene derivative, which is a flame retardant suitable for the present invention, is not added and the modified polyolefin is added, the adhesive performance with the aluminum foil is good, but the flame retardant performance is insufficient. It was.
Moreover, although the modified polyolefin was not added and the flame retardant suitable for this invention was added for the comparative example 3, the flame retardance performance was sufficient, but the adhesive performance with an aluminum foil was inferior.
In Comparative Examples 4 to 6, since the flame retardant suitable for the present invention is not added, it is clear from Table 2 that the balance between the flame retardant performance and the adhesive performance is poor. In particular, Comparative Examples 4 to 5 use magnesium hydroxide as a flame retardant and thus have poor flame retardant performance. Despite the addition of an appropriate amount of modified polyolefin, the adhesive performance with aluminum foil is very poor. It was. This is probably because the flame retardant is bleeding on the fiber surface.
In Comparative Example 6, a flame retardant combining antimony trioxide and a halogen-based flame retardant was added, and modified polyolefin was also added, but the flame retardant performance was good, but the adhesion performance to the aluminum foil was slightly inferior. It was. In addition, since halogen-based flame retardants are used, it is expected that combustion gas that significantly harms the environment is generated when incinerated.
Reference Examples 1 and 2 in Table 2 use a flame retardant suitable for the present invention, but because of the excessive addition amount, a strange odor is found around the spinning tower during spinning, and the yarn during spinning Cutting frequently occurred, the spinnability was remarkably lowered, and the fiber workability was remarkably deteriorated.

As described above, the functional fiber of the present invention or the functional fiber molded body using the functional fiber has high flame retardancy, has little adverse effect on the environment, can maintain strong adhesiveness, and can be used for a long time. It can be widely used for bonding various products such as automobile interior materials, building materials, interior materials, filter materials and the like.
In recent years, in the fields of aircraft, ships, automobiles and other transportation equipment, electrical and electronic materials, civil engineering and building materials, the need for flame retardant materials has increased, and accordingly flame retardant materials have been bonded. The adhesive material is also required to be flame retardant.

Explanatory drawing showing the configuration of the peel strength test sample Explanatory drawing showing how to perform peel strength test

Claims (9)

Thermoplastic containing modified polyolefin graft-polymerized with at least one vinyl monomer (hereinafter referred to as modifier) selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride and nitrogen-containing phosphorus compound A functional fiber obtained by using a resin , wherein the thermoplastic resin is selected from polyolefin, polyester, or polyamide, and the nitrogen-containing phosphorus compound is a cyclic phosphazene derivative represented by the formula (1) and the formula ( A functional fiber, which is at least one phosphazene derivative selected from the group consisting of the chain phosphazene derivatives represented by 2).

In Formula (1), m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of alkoxyl, aryloxy and amino.
In the formula (2), n is an integer of 3 to 10, and Q is a group independently selected from the group consisting of alkoxyl, aryloxy and amino . The functional fiber is a composite fiber composed of a second component made of a thermoplastic resin containing a modified polyolefin and a first component made of a thermoplastic resin having a higher melting point than the second component, wherein the second component is 2. The composite fiber according to claim 1, wherein at least a part of the surface of the composite fiber is continuously formed in the length direction, and the first component and / or the second component contains a nitrogen-containing phosphorus compound. The functional fiber described. Nitrogen-containing phosphorus compounds, functional fiber relative to 0.25-5% by weight of the functional fiber of claim 1 or one of claims 2, characterized in that it is contained in the range. Equation (3) hindered amine derivative having a group represented by is any one of claims 1 to 3, characterized in that it is further contained in an amount of 0.1 to 3% by weight relative to the functional fiber The functional fiber described.

In the formula (3), R ¹ is alkyl having 1 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, bicyclic or tricyclic hydrocarbon having 7 to 12 carbon atoms, and 7 to 15 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ are groups independently selected from the group consisting of alkyls having 1 to 4 carbon atoms, or R ² and R ³ and / or pentamethylene in which R ⁴ and R ⁵ are bonded, R ⁶ is alkoxy having 1 to 4 carbon atoms, aryloxy having 6 to 12 carbon atoms, amino having 1 to 18 carbon atoms, represented by the formula (4) A represents oxygen or N—R ⁷ , and R ⁷ represents a group selected from the group consisting of hydrogen and linear or branched alkyl having 1 to 12 carbons. is there.
Here, in formula (4), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and A are the same as in formula (3).   The modifier is at least one selected from the group consisting of maleic acid, acrylic acid, methacrylic acid and anhydrides thereof, and the modifier is in the range of 0.001 to 2 mol / kg with respect to the functional fiber. The functional fiber according to claim 1, wherein the functional fiber is contained. The functional fiber according to any one of claims 1 to 5 , wherein the functional fiber is a polyolefin-based fiber. The functional fiber according to claim 1, wherein the thermoplastic resin is polyester. The functional fiber according to claim 2, wherein the thermoplastic resin of the first component is polyester.   The fiber molded object using the functional fiber of any one of Claims 1-8.

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