JPH11200157A - Elastic composite filament excellent in fire retardant property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite polyester elastic filament excellent in dynamic characteristics and elastic recovery, and also in fire retardant property, heat resistance, weather resistance and creep characteristics, and most suitable for various uses as an industrial material. SOLUTION: This elastic composite filament, excellent in fire retardant property is a composite filament consisting of 2 components one of which is a thermoplastic polyester block copolymer consisting of an aromatic dicarboxylic acid as a main acid component, an aliphatic and/or alicyclic hydroxy compound as a main diol component, and further obtained by copolymerizing phosphorus atom content 500-50,000 ppm with a low melting polymer segment having 400-6000 molecular weight, and has >=80% breaking elongation, >=0.5 g/d breaking strength and >=90% elongation recovery after stretching by 30% at 80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a variety of industrial materials such as ropes, fishing nets, nets, office and vehicle chairs, and multi- or monofilaments which can be used in the textile field. The present invention relates to a polyester elastic filament having excellent flame retardancy, heat resistance, coloring properties, weather resistance, elongation recovery properties and tensile properties.

[0002]

2. Description of the Related Art Ropes, fishing nets, and the like, which have molecular orientation filaments composed of a thermoplastic polyester block copolymer having relatively high tensile strength and excellent recovery characteristics against high elongation and bending deformation, can be used.
When it is intended to be applied to industrial materials such as high-performance office and vehicle chairs, which can be used as substitutes for conventional cushioning materials such as urethane, using their elastic properties as nets or fabrics, for example, It is known that its flame retardancy, weather resistance, and heat aging resistance are less stable than use of polyester and other fibers, and these properties limit the above applications. .

Here, as a technique for improving the flame retardancy of a filament made of a thermoplastic polyester block copolymer, an organic halogen compound such as hexabromobenzene or decabromophenyl ether is added to the copolymer and a flame retardant aid is used. It has been conventionally known to use an inorganic compound such as antimony trioxide in combination.

However, in such a method, when the filament is used for a long period of time outdoors, for example, the flame retardant bleeds out, resulting in poor appearance, and the flame retardant effect is lost due to heat or light deterioration, and the flame retardant may become flammable. In addition, there is a problem in that mechanical properties such as elongation recoverability and relatively high strength, which are characteristics of filaments made of a thermoplastic polyester block copolymer, are impaired.

To solve the problems of flame retardancy and retention stability, a method of adding a high molecular weight halogenated bisphenol A type phenoxy resin and an inorganic flame retardant auxiliary (Japanese Patent Publication No. 4-14132), A method of adding a brominated epoxy resin (Japanese Patent Publication No. 53-18068) has been proposed. However, even in these cases, when imparting flame retardancy, it is necessary to add a large amount of the above flame retardant,
There are problems such as molding failure due to gelation during high-temperature molding, mechanical property deterioration due to light, and particularly, elongation recovery property is deteriorated.

Further, for the purpose of improving the above-mentioned problems, there is a method of adding a substance imparting flame retardancy during the production of a polymer to copolymerize the polymer. -41610) has been proposed. However, in these cases, there were problems such as insufficient expected flame retardancy.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide excellent flame retardancy, weather resistance and heat aging resistance.
Moreover, an object of the present invention is to provide a thermoplastic polyester-based elastic filament which is excellent in mechanical properties such as elongation recovery in a shape in which the filament is used.

[0008]

According to the present invention, an aromatic dicarboxylic acid is used as a main acid component, an aliphatic and / or alicyclic dihydroxy compound is used as a main glycol component, and a phosphorus atom content is 400 to 6000 in molecular weight. A two-component composite filament comprising a thermoplastic polyester block copolymer obtained by copolymerizing 500 to 50,000 ppm with respect to the low-melting polymer segment having a breaking elongation of 80% or more and a breaking strength of 0. An elastic composite filament excellent in flame retardancy, characterized in that the elongation recovery after 30% elongation at 80 ° C. is at least 90%, and an aromatic dicarboxylic acid as a main acid component. ,
An aliphatic and / or alicyclic dihydroxy compound is used as a main glycol component, and further, a phosphorus atom content has a molecular weight of 40.
500 to 6000 low melting point polymer segment
A composite filament composed of two components comprising a thermoplastic polyester block copolymer containing a triazine compound and / or a derivative thereof as a component and a thermoplastic polyester block copolymer obtained by copolymerizing 50,000 ppm, Furthermore, the thermoplastic polyester block copolymer is an elastic composite filament having excellent flame retardancy, wherein the limiting oxygen index (LOI) is 20 or more.
And the flame-retardant elastic filament according to the above, wherein the thermoplastic polyester block copolymer is preferably obtained by copolymerizing a phosphorus compound represented by the following general formula (I):

[0009]

Embedded image (Wherein, R1, is a monovalent ester-forming functional group,
R2 and R3 are the same or different groups, and each is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms,
A is selected from 1, and A represents a divalent or trivalent organic residue. N1 represents 1 or 2, and n2 represents an integer of 0 to 4. And the triazine-based compound and / or a derivative thereof comprises a flame-retardant polyester block copolymer composition represented by the following general formulas (II) to (IV). The composite elasticity having excellent flame retardancy as described above, wherein the excellent elastic filament and the composite filament have a substantially sheath-core shape, and the area ratio of the core portion to the fiber cross-sectional area is 50% or more. The melting point of the filament and the core component is 150 ° C. or more and less than 200 ° C., and the melting point of the sheath component is 20 ° C. or more and less than 50 ° C. lower than the melting point of the core component. 2. The flame retardant according to claim 1, wherein the thermoplastic polyester block copolymer according to claim 1 is used as a polymer constituting an excellent composite elastic filament and a sheath portion. The flame-retardant flame retardant according to the above, wherein the thermoplastic polyester block copolymer constituting the composite elastic filament and the sheath portion contains carbon black in an amount of 0.1% by weight or more based on the copolymer. A composite elastic filament having excellent properties.

[0010]

Embedded image

[0011]

Embedded image

[0012]

Embedded image (Wherein R1, R2, and R3 are a hydrogen atom, an amino group, an alkyl group, an annealed group, and a phenyl group;
3 may be the same or different. )

The thermoplastic polyester block copolymer which is a raw material of the filament in the present invention is a copolymer comprising a high-melting-point hard polyester segment and a low-melting-point polymer segment having a molecular weight of 400 to 6000, and a high-melting-point polyester segment. A thermoplastic polyester block comprising a component having a melting point of 150 ° C. or more when a high polymer is formed only with the constituent components and a melting point or softening point of 80 ° C. or less when measured only with the low melting polymer segment constituent components. It is a copolymer.

The polyester block copolymer, which is a raw material of the filament, will be described in more detail. For example, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalene An aromatic dicarboxylic acid such as dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, bis (4-carboxyphenyl) methane, bis (4-carboxyphenyl) sulfone or an ester thereof;

[0015] Ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, 2,2-dimethyltrimethylene glycol, hexamethylene glycol, decamethylene glycol, p-
Polyester produced from diols such as xylylene glycol and cyclohexanedimethanol, or copolyesters using two or more of these dicarboxylic acids or two or more diols

Polyesters derived from oxy acids such as p- (β-hydroxyethoxy) benzoic acid and esters thereof, polylactones such as polypivalolactone, 1,2-bis (4,4'-dicarboxyphenoxy) Examples thereof include polyether esters produced from aromatic ether dicarboxylic acids such as ethane and the aforementioned diols, and copolyesters obtained by combining the above dicarboxylic acids, oxy acids, and diols.

The low-melting-point polymer segment having a molecular weight of 400 to 6000 includes, for example, polyalkylene ether glycols such as poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, and mixtures thereof. Further, copolymerized polyether glycols obtained by copolymerizing these polyether glycol constituents can be shown. Polyesters prepared from aliphatic dicarboxylic acids having 2 to 12 carbon atoms and aliphatic glycols having 2 to 10 carbon atoms, for example, polyethylene nadipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebacate, poly Examples thereof include tetramethylene dodecane, polytetramethylene azelate, polyhexamethylene azelate, poly-ε-caprolactone, and the like. Further, a polyester polyether copolymer obtained by combining the above polyester and polyether can also be shown. In the polyester block copolymer, the ratio of the low-melting-point polymer component is 5 to 80.
% By weight, more preferably 20 to 50% by weight.

The above-mentioned polyester has a phosphorus atom content of 50.
The following general formula (I) so as to be 0 to 50,000 ppm.
And adding a phosphorus compound represented by the formula:

[0019]

Embedded image (Wherein, R1, is a monovalent ester-forming functional group,
R2 and R3 are the same or different groups, and each is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms,
A is selected from 1, and A represents a divalent or trivalent organic residue. N1 represents 1 or 2, and n2 represents an integer of 0 to 4. )

In the present invention, the phosphorus compound used for obtaining the polymer composition used as a raw material of the flame-retardant thermoplastic elastomer filament is the one represented by the above (I). A carboxyl group, an alkyl ester having 1 to 6 carbon atoms in the carboxyl group,
Examples thereof include a cycloalkyl ester, an annealed ester, a hydroxyl group, and a hydroxylalkoxycarbonyl group having 2 to 7 carbon atoms.

R2 and R3 are preferably a halogen atom such as a chlorine atom or a bromine atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an annealing group or the above-mentioned monovalent group of R1. It is listed as. On the other hand, preferred as A are lower alkylene groups such as methylene, ethylene, 1,2-propylene and 1,3 propylene,
It may be an arylene group such as 1,3-phenylene or 1,4-phenylene, a divalent group such as 1,3-xylylene or 1,4-xylylene, or a trivalent or higher group. The above hydrocarbon group may be substituted by a halogen group such as a chlorine atom and a bromine atom.

In the present invention, the phosphorus compound represented by the general formula (I) contains 500 to 50 as a phosphorus atom in the polymer.
It is appropriate to use so as to contain 000 ppm,
Particularly, it is preferable to use 1000 to 10000 ppm. When the amount of the phosphorus compound used is smaller than the above range, an expected flame-retardant thermoplastic elastomer cannot be obtained. On the other hand, when the amount used is larger than the above range, the mechanical strength is unfavorably poor.

These polyester block copolymers can be produced by a usual polycondensation method. A preferred method is to heat an aromatic dicarboxylic acid or its dimethyl ester, a low melting segment forming diol and a molecular weight diol to a temperature of about 150-260 ° C. in the presence of a catalyst, and then form by a polycondensation or transesterification reaction. A method of removing a water or methanol, heating the resulting prepolymer under vacuum to remove excess low molecular weight diol to obtain a polyester type block copolymer having a high degree of polymerization, a pre-adjusted high melting polyester. A segment-forming prepolymer and a low-melting polymer A segment-forming prepolymer is mixed with a bifunctional compound that reacts with the terminal functional group of the prepolymer, and then the system is kept at a high vacuum to remove volatile components. To obtain a polyester block copolymer, The polyester and lactone monomer heated and mixed, and a method of the lactone while opening polymerization ester block copolymer.

The phosphorus compound may be added at the time of transesterification, before the polycondensation after transesterification or at a relatively early stage of the polycondensation reaction. Is not limited.

In the present invention, in addition to the above-mentioned thermoplastic polyester block copolymer, the following general formulas (II) to (IV)
May be added.

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image (Wherein R1, R2, and R3 are a hydrogen atom, an amino group, an alkyl group, an annealed group, and a phenyl group;
3 may be the same or different. )

Further, as a derivative of the triazine compound, an isocyanate group-containing compound represented by the following general formula can also be mentioned. R1- (NCO) n (where n = 1 to 4, the structure of R1 is arbitrary.) Of these, the most common ones are MDI, TD
It is used as a raw material for urethane such as I. Among these, melamine cyanurate, which is an adduct of melamine and cyanuric acid, is particularly preferred from the viewpoint that the physical properties of the polyester block copolymer are not reduced and blooming does not occur. More preferably, it is a powdered melamine cyanurate, and the average particle size of the approximate powder when the image of the approximate powder taken by a scanning electron microscope (SEM) is analyzed by an image analyzer is 2 μm to 100 μm. The addition amount of the triazine-based compound and / or its derivative may be, for example, a polyester block copolymer, 10
0.5 to 20 parts by weight with respect to 0 parts by weight is preferred. Particularly, 1 to 5 parts by weight is preferable from the viewpoint of flexibility and flame retardancy.

As a method for adding the phosphorus compound, the phosphorus compound may be added during the transesterification reaction, before the polycondensation after the transesterification or at a relatively early stage of the polycondensation reaction, or may be added by a heating roll or extrusion. Can be mixed using a kneader such as a kneader or a Banbury mixer, and the addition method is not particularly limited.

Further, the composition of the present invention may contain, as additives, known antioxidants such as hindered phenol, sulfur, and phosphorus, hindered amine, triazole, benzophenone, benzoate, nickel, salicyl. -Based light stabilizers, antistatic agents, lubricants, molecular regulators such as peroxides, metal deactivators, organic and inorganic nucleating agents, neutralizing agents,
One or more antacids, antibacterial agents, optical brighteners, fillers, flame retardants, flame retardant auxiliaries, and the like can be added.

Hindered phenolic antioxidants include 3,5-di-t-butyl-4-hydroxy-toluene, n-octadecyl-β- (4′-hydroxy-
3 ', 5'-di-t-butylphenyl) propionate, tetrakis [methylene-3- (3', 5'-di-t
-Butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6'-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, calcium (3,5-di-t-butyl-4-hydroxy-benzyl-monoethyl-phosphate), triethylene glycol-bis [3- (3-
t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2
-{Β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4
8,10-tetraoxaspiro [5,5] undecane,
Bis [3,3-bis (4'hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, tocopherol, 2,2'-ethylidenebis (4,6-di-t-butylphenol), N, N ' -Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl]
Hydrazine, 2,2′-oxamidobis [ethyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 1,1,3-tris (2-methyl-
4-hydroxy-5-t-butylphenyl) butane,
1,3,5-tris (3 ′, 5′-di-t-butyl-
4'-hydroxybenzyl) -S-triazine-2,
4,6 (1H, 3H, 5H) -trione, 1,3,5-
Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-t-
Butyl-4-hydroxyhydrocinnamic acid triester with-1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4,6 (1H, 3H,
5H) and the like.

As the sulfur-based antioxidant, dilauryl-
3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate ester,
Examples thereof include dioctadecyl sulfide and pentaerythritol-tetra (β-lauryl-thiopropionate) ester.

Examples of the phosphorus-based antioxidant include tris (mixed, mono- and dinolylphenyl) phosphite, tris (2,3-di-t-butylphenyl) phosphite, and 4,4'-butylidene-bis ( 3-methyl-6-t
-Butylphenyl-di-tridecyl) phosphite,
1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl) butane, bis (2,4di-tert-butylphenyl) pentaerythritol-di-phosphite , Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenephosphanite, bis (2,6-di-t-butyl-4-methylphenyl) pentaeristol-di-phosphite 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) -2-ethylhexyl-phosphite, bis (2,4,6-di-t-butylphenyl) pentaerythritol-di-phosphite Phyte, triphenyl phosphite, diphenyl decyl phosphite, didecyl phenyl phosphite, tridecyl phosphite, trioctyl phosphite , Tri-dodecyl phosphite,
Trioctadecyl phosphite, trinonyl phenyl phosphite, tridodecyl trithio phosphite and the like can be mentioned.

The hindered amines include polycondensates of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperodine, poly [[6- (1 , 1,3,3-Tetrabutyl) imino-1,3,5-triazine-2,4-diyl] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imyl]], 2- bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester of n-butylmalonic acid, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,3 4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene With diamine Polycondensate with 1,2-dibromoethane, poly [(N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine)-(4-monophorino-1,3 , 5-triazine 2,
6-diyl) -bis (3,3,5,5-tetramitylpiperazinone), tris (2,2,6,6-tetramethyl-4-piperidyl) -dodecyl-1,2,3,4- Butanetetracarboxylate, tris (1,2,2,6,
6-pentamethyl-4-piperidyl) -dodecyl-1,
2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,6,11-tris [@ 4,6-bis (N-butyl- N- (1,2,2,6,6-pentamethylpiperidin-4-yl) amino-1,3,5-triazin-2-yl {amino] undecane, 1- [2-
[3-5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy] -2,2,6,6-tetromethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2 , 4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine,
N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,
6,6-pentamethyl-4-piperidyl) amino] -6
-Chloro-1,3,5-triazine condensate and the like.

Light stabilizers such as triazole, benzophenone, benzoate, nickel, and salicylic acid light stabilizers such as triazole, benzophenone, benzoate, nickel, and salicylic acid light stabilizers include
2'-dihydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-n-octoxybenzophenone, p
-T-butylphenyl salicylate, 2,4-di-t-
Butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di -T-amylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-
Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2,5-bis- [ 5′-t-butylbenzoxazolyl- (2)]-thiophene, [bis (3,5-di-t-
Butyl-4-hydroxybenzylphosphoric acid monoethyl ester] nickel salt, 2-ethoxy-5-t-butyl-2 '
-Ethyl oxalic acid-bis-anilide 85-
A mixture of 90% and 2-ethoxy-5-t-butyl-2'-ethyl-4'-t-butyloxalic acid-bis-anilide 10-15%, 2- (3,5-di-t-butyl) -2-hydroxyphenyl) benzotriazole,
2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole,
2-ethoxy-2'-ethyloxalic acid bisanilide, 2- [2'hydroxy-5'-methyl-3 '
-(3 ", 4", 5 ", 6" -tetrahydrophthalimido-methyl) phenyl] benzotriazole,
Bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2- (2'-hydroxy-5'-t
-Octylphenyl) benzotriazole, 2-hydroxy-4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, and the like.

As the antistatic agent, glycerin fatty acid (C8-C22) ester, sorbitan fatty acid (C8-C22)
C22) ester, propylene glycol fatty acid (C8
~ C22) Ester, sucrose fatty acid (C8 ~ C22)
Ester, citric acid mono (di or tri) stearyl ester, pentaerythritol fatty acid (C8-C18) ester, trimethylolpropane fatty acid (C8-C1)
8) S, polyglycerin fatty acid (C8-C22)
Ester, polyoxyethylene (20 mol) glycerin fatty acid (C12-C18) ester, oilyoxyethylene (20 mol) sorbitan fatty acid (C12-C18)
Esters, polyethylene glycol fatty acids (C8-C2
2) Ester, polyoxyethylene fatty alcohol (C
12-C20) ether, polyoxyethylene (4-5
0 mol) alkyl (C4 or more) phenyl ether, N,
N-bis (2-hydroxyethyl) fat (C8-C1
8) Nonionic surfactants such as amines, condensation products of fatty acids and diethanolamine, polyoxypropylene polyoxyethylene block polymers, polyethylene glycol and polypropylene glycol; alkyl (C
10-C20) sulfonate (Na, K, NH4), alkyl naphthalene sulfonate (Na), sodium dialkyl (C4-C16) sulfonate, alkyl (C8-C20) sulfate (Na, K, NH)
4), fatty acid (C8-C22) salts (Na, K, NH4)
N-acyl (C8 to C1)
8) Zwitterionic surfactants such as sarcosinate; and other auxiliaries such as polyacrylic acid and its sodium salt.

Examples of the lubricant include hexylamide, octylamide, stearylamide, oleylamide, ercylamidoethylenebisstearylamide, laurylamide, behenylamide, methylenebisstearylamide,
C3-C30 saturated or unsaturated aliphatic amides and derivatives thereof such as ricinolamide; butyl stearylate;
C3-C30 saturated or unsaturated aliphatic esters such as isobutyl stearate and the like and derivatives thereof; commercially available silicone release agents; silicone compounds such as silicone oil and silicone gum; commercially available fluorine-based release agents; And fluorine compounds such as ethylene nitride.

Examples of the metal deactivator include 3-N'-salicyloylamino-1,2,4-triazole, salicylaldehyde, salicylhydrazine, N, N'-bis- [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, oxalyl-bis [benzylidene hydrazide], 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, , 4,5,6-dibenzo-1,2-oxaphosphane-2-oxide, tris [2-t-butyl-4
-Thio (2'-methyl-4'-hydroxy-5-t-butyl) phenyl-5-methyl] phenylphosphite, 2,2'-oxamido-bis- [ethyl-3 (3
5-di-t-butyl-4-hydroxyphenyl) propionate].

As the nucleating agent, 1,3,2,4-di-benzylidene-sorbitol, 1,3,2,4-di-di-di-
(P-methyl-benzylidene) sorbitol, 1,3
2,4-di- (p-ethyl-benzylidene) sorbitol, 1,3,2,4-di- (2 ′, 4′-di-methyl-
Benzylidene) sorbitol, 1,3-p-chloro-benzylidene-2,4-p-methyl-benzylidene-sorbitol, 1,3,2,4-di- (p-propyl-benzylidene) sorbitol, aluminum-mono-hydroxy -Di-pt-butylbenzoate, sodium-bis (4-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis- (4,6-di-t-butyl-phenyl) phosphate , Talc, sodium benzoate, lithium-2,2'-methylene-bis-
(4,6-di-t-butylphenyl) phosphate and the like.

As the neutralizing agent and the antacid, lithium stearate, 1,2-hydroxylithium stearate,
Sodium stearoyl lactate, sodium stearate, potassium stearate, lithium behenate, lithium montan, sodium behenate, sodium montanate, calcium stearyl lactate, calcium behenate, calcium montanate, cadmium stearate, cadmium laurate, cadmium ricinoleate , Barium naphthenate, barium 2-ethylhexoate, barium stearate, barium 2-ethylhexoate, calcium stearate, calcium laurate, calcium ricinoleate, strontium stearate, zinc stearate, zinc laurate, zinc ricinoleate, 2- Zinc ethylhexoate, zinc stearate, dibasic lead stearate, lead naphthenate, tin stearate, aluminum stearate, Alkali or alkaline earth metal salts of higher fatty acids such as magnesium thearate, alkyl lactic acid; basic magnesium aluminum hydroxy carbonate hydrate (hydrotalcite), basic zeolite, epichlorohydrin and bisphenol A polymers, Examples include epoxidized soybean oils, epoxidized fatty monoesters, epoxidized alicyclic fatty acid esters, polycarbodiimides, and isocyanate compounds.

As the filler, carbon black, magnesium oxide, aluminum oxide, silicon oxide, calcium oxide, titanium oxide, chromium (III) oxide, iron oxide, zinc oxide, silica, diatomaceous earth, alumina fiber, antimony oxide, barium ferrite , Strontium ferrite, beryllium oxide, pumice, oxides such as pumice balloons, magnesium hydroxide, aluminum hydroxide, basic substances such as basic magnesium carbonate or hydroxides; magnesium carbonate,
Carbonates such as calcium carbonate, barium sulfate, ammonium sulfate, calcium sulfite, dolomite, dawsonite; (sulfite) sulfates such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, basic magnesium sulfate; sodium silicate, magnesium silicate, aluminum silicate , Potassium silicate, calcium silicate, talc, clay, mica, asbestos, silicates such as glass fiber, montmorillolite, glass balloon, glass beads, pentonite; kaolin (porcelain earth), pearlite, iron powder, copper powder, lead powder , Aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, zinc borate, aluminum borate, barium metaborate, calcium borate, sodium borate, and the like. In particular, for the purpose of improving the light resistance deterioration of the filament, carbon black is preferable as a light shielding effect particularly in a monofilament shape.

The elastic filament having the above composition must have a breaking elongation of 80% or more, a breaking strength of 0.5 g / d or more, and an elongation recovery after 30% elongation at 80 ° C. of 90% or more. . That is, if the elongation at break is less than 80%, there arises a problem that proper elastomeric characteristics cannot be exhibited. Preferably it is 100% or more. Further, if the breaking strength is less than 0.5 g / d, there is a problem that the formed fabric has insufficient strength and cannot withstand a static load. Preferably 0.8 g / d or more, more preferably 1.5 g / d
However, if the fiber strength exceeds 4.0 g / d, the initial load gradient of the fabric rises, which is not preferable in terms of fabric design. Further, the elongation recovery rate after 30% elongation at 80 ° C. is very important from the viewpoint of durability as a cushioning material. If it is less than 90%, elastic properties are reduced by repeated use and the fabric is slackened. It is not desirable on the product. From such a viewpoint, a preferable elastic recovery rate is 95% or more.

Of the above compositions, a polymer comprising a thermoplastic polyester block copolymer containing a triazine compound and / or a derivative thereof must have a limiting oxygen index of 20 or more. If the limiting oxygen index is less than 20, only an insufficient effect on the flame retardancy can be obtained.

Further, in the present invention, there is provided a composite elastic filament characterized in that the filament has a substantially sheath-core shape and the area ratio of the core portion to the fiber cross-sectional area is 50% or more. The melting point of the core component is 150 ° C. or more and less than 200 ° C., and the melting point of the sheath component is 20 ° C. or more and 50 ° C. higher than the melting point of the core component.
The composite elastic filament is characterized by using the thermoplastic polyester block copolymer as a lower component, specifically, as a sheath component. Here, the sea core shape may have a concentric array of cross-sectional shapes, and the center may be eccentric. In an extreme case, the core component may be partially exposed on the surface, but it is preferable that the sheath component is at least 50%, more preferably at least 70%, of the average surface area of the fiber. .

Here, as one of the effects of the present patent, these various additives may be added to either the sheath or the core, but may be a flame retardant, a light / absorbent, a lubricant, an antibacterial agent, etc. In particular, when the effect is improved by blending it on the fiber surface, by blending more in the sheath part, the amount of additives can be saved and it is not only economical, but also the conventional case where a large amount of it is required. It is possible to remarkably improve the reduction of mechanical properties such as strength, which was a problem. This effect is most effective, for example, by adding an addition amount that was conventionally difficult to impair the mechanical properties of the yarn to the sheath portion and not adding it to the core portion at all. It has advanced functions such as flame retardancy, light resistance, smoothness, and antibacterial properties, and the core has mechanical properties such as strength and elasticity. In fact, the flame retardancy level of the yarn according to the invention is at a level far exceeding that of conventional polyester-based elastic filaments.

When using such a copolymerized elastomer, it should be noted that the mechanical properties of the original elastomer due to the copolymerization, especially the reduction of the elongation recovery property upon repeated deformation, and the permanent set remaining when a constant load is applied for a long time, That is, the so-called creep characteristics are reduced. As already mentioned,
According to this patent, by using a two-component polymer and arranging it in a so-called sea-score shape, it is possible to adjust the copolymerization concentration of both and the amount of additives, and to provide various functions. Is possible. For example, it is preferable to reduce the copolymerization amount and the addition amount of the polymer disposed in the core portion that greatly affects the elongation recovery characteristics and the creep performance. In addition, it is preferable to increase the flame retardant and the copolymerization amount in the sheath portion which directly receives a flame or light. In particular, a sufficient effect can be expected if an inorganic additive such as carbon black is blended only in the surface layer as a light-shielding effect. Here, the ratio of the sheath portion to the core portion is important, and is preferably 50% or more and 70% or more in order to maintain the mechanical properties.
In addition, a difference is given to the melting point of the elastomer between the sheath portion and the core portion, that is, for example, a fiber is finished into a fabric, and then the sheath portion set at a low melting point is partially fused to improve the form stability as the fabric. Means can also be taken as needed.

[0048]

EXAMPLES The present invention will be described below with reference to examples. Example 1 Polymer A: 60 parts of dimethyl terephthalate, 1,4-
38 parts of butanediol, 37 parts of poly (tetramethylene oxide) glycol having a molecular weight of about 1000, and a phosphorus compound (V) represented by the following formula:

[0049]

Embedded image The resulting polymer was added so as to have a concentration of 10000 ppm, tetrabutyl titanate was used as metal titanium as a catalyst so as to be 150 ppm with respect to the polymer to be formed, and transesterification was performed at 150 to 230 ° C. Next, a hindered phenol-based stabilizer [Ciba Geigy Co., Ltd. product; Irgan]
ox1010] in an amount of 0.2 part by weight as a slurry of 1,4-butanediol, respectively, and subjected to melt polymerization at 230 to 250 ° C. under a reduced pressure of 3 torr or less to obtain polymers. Furthermore, using a twin screw extruder,
Triphenyl phosphate, 10 parts, melamine cyanurate, 3
And 0.2 parts of carbon black were added to obtain the desired polymer. The LOI value of the obtained polymer was 23.

On the other hand, as the polymer B, 60 parts of dimethyl terephthalate, 38 parts of 1,4-butanediol, 37 parts of poly (tetramethylene oxide) glycol having a molecular weight of about 1,000, and tetrabutyl titanate as metal titanium as a catalyst were used as the polymer to be formed. 150 ppm
And transesterified at 150 to 230 ° C. Then, a hindered phenol-based stabilizer [Ciba Geigy Co., Ltd. product; Irga]
Nox1010] 0.2 parts by weight of each was added as a slurry of 1,4-butanediol, and melt polymerization was performed at 230 to 250 ° C. under a reduced pressure of 3 torr or less to obtain a desired polymer. The surface hardness of the obtained polymer is 46,
The LOI value was 19.

Degree of vacuum of 0.1 mmHG, 80 ° C.
After pre-drying for 4 hours under the same atmosphere temperature, a drying treatment was performed at 120 ° C. for 12 hours under the same vacuum conditions. The dried resin is subjected to a two-component resin by using a spinning machine having a composite nozzle portion composed of a double tube previously set to be polymer A in the sheath portion and polymer B in the core portion and two pairs of melt extrusion devices. They are separately melted, and the discharge amount is adjusted so that the area ratio of the sheath and the core is 20:80 at the meeting portion, and the total discharge amount of both is 22.2 g / min per nozzle hole (unit of monofilament). It was adjusted to be. In each of the resin combinations described above, a temperature about 20 ° C. higher than the melting point of the resin disposed in the core portion was set as the temperature of the associated portion, and spinning was performed at each level. The state of the spun yarn was stable in all combinations. The discharged polymer is cooled by passing through a water tank of about 30 ° C. installed with an air gap of 50 mm, and then a Nelson roller having a surface temperature controlled at 90 ° C. and a speed of 20 m / min. The film was stretched 4 times between the roller and a take-up roller, and subsequently taken up by another pair of Nelson rollers while being relaxed by about 2% between slit type heaters set to a length of 150 ° C., and immediately wound up. . The denier of the final yarn was about 2500 denier, and a seascore-shaped composite yarn having a concentric concentric shape as observed in the cross-sectional shape was obtained. Excellent results were obtained for both the mechanical properties and the flame retardant properties.

Example 2 A desired yarn was obtained by performing the same polymerization and spinning operations as in Example 1 except that the amount of melamine cyanurate in Polymer A of Example 1 was changed to 8 parts (referred to as polymer C). Flame retardancy has been further improved.

Example 3 A filament was prepared in the same manner as in Example 1, except that triphenyl phosphate and melamine cyanurate were not added (only 0.2 part of carbon black was added). LOI of used polymer (Polymer D)
The value is 22, which is slightly inferior to Example 1, reflecting the slightly inferior flame retardancy of Example 1. However, the yarn-making properties are extremely good, and a yarn having excellent mechanical properties, particularly excellent recovery properties, can be obtained. Was.

Comparative Example 1 Polymer D: 60 parts of dimethyl terephthalate, 1,4-
38 parts of butanediol, 37 parts of poly (tetramethylene oxide) glycol having a molecular weight of about 1000, and tetrabutyl titanate as a metal titanium as a catalyst were added at a concentration of 150 ppm based on the produced polymer.
The transesterification was performed at 50-230 ° C. Next, a hindered phenol-based stabilizer [Ciba.
Geigy Corporation product; Irganox 1010] 0.2
Parts by weight, respectively, as a slurry of 1,4-butanediol, and 230-250 under reduced pressure of 3 torr or less.
Melt polymerization was carried out at ℃ to obtain a polymer. The LOI value of the obtained polymer (Polymer E) was 19. Using this polymer as a raw material for both the sheath and the core, a monofilament was prepared in the same manner as in Example 1. Although the mechanical properties were reasonably good, the heat resistance and light resistance were significantly reduced.

Comparative Example 2 A monofilament was prepared by performing exactly the same operation as in the example except that the same polymer C was used for the sheath portion and the core portion.
A filament having a substantially uniform cross section could be obtained. Although the flame retardancy was at a good level, the mechanical properties were reduced, possibly due to the large amount of the additive, and the elongation recovery was particularly reduced as compared with the examples.

[0056]

[Table 1]

(Evaluation Method) The evaluation methods described in the specification and examples of the present invention will be described. (Limited oxygen index (LOI) method of polymer) JIS, K7201 (A
(No.-1) Method (Strength and elongation characteristics) Using a Tensilon TM measuring device manufactured by Orientec, a sample length of 100 mm was measured at a strain rate of 100% / min under an atmosphere of 25% temperature and 65% relative humidity. The breaking strength and elongation were evaluated from the obtained strain / stress curves. In each measurement, the average value of five measurements was used as the value. (Elongation recovery rate) A heating tank adjusted to a temperature of 80 ° C. was installed in the above measuring device, and after setting the sample length to 100 mm in the same manner,
After heating for 2 minutes, it was stretched to 30% at a strain rate of 100% / min and immediately returned to 0% at the same rate. Ten seconds after the deformation returned, elongation deformation of up to 30% was applied again at the same strain rate. From the series of strain / stress curves recorded at this time, 2
The amount of strain (x%) at which stress starts to be generated by the second elongation was determined, and elongation recovery was evaluated by the following equation. Elongation recovery rate (%) = 100-x (flame retardancy) The fibers obtained in each experiment were plied so as to have a denier of about 2500, and each of the warp yarns (Example 1 and Comparative Example 1 were used as they were). And a plain woven fabric was prepared so as to have a driving density of 25 fibers / inch, and a combustion test was conducted. The flammability test is basically based on JIS-L1
091 A2 method (Meckelburner method). That is, each of the weft and the weft passes through the woven fabric in the longitudinal direction.
mm x 250 mm, and burn test with n = 3 each
It was carried out under the same conditions as in IS, and the longest carbonization distance at a total of n = 6 was used as an index of flame retardancy. 1 / 100gf load of each fineness in the oven of 1
The mixture was allowed to stand for 0 minute, and at a predetermined temperature, a 50 cm center interval of the fiber was marked. Subsequently, the initial load of the fiber was removed, and a load previously calculated so that the fiber was stretched by 15% at room temperature was immediately applied, and the length between the markings immediately after that was measured (L1). After 24 hours with the oven maintained at the above temperature, the length was measured again (L2). The creep rate at a high temperature was determined by the following equation. Creep rate (%) = 100 × (L2−L1) / L1 (Light resistance) The above tensile test of the yarn after 400 hours of irradiation at 85 ° C. under the conditions of a discharge voltage of 135 V and a current of 16 A using an ultraviolet carbon fade meter. The light fastness was evaluated based on the retention rate of the untreated yarn having the strength in the above.

[0058]

According to the present invention, it is possible to provide an elastic filament excellent in flexibility, flame retardancy, molding retention stability, creep characteristics and appearance.

Claims (8)

[Claims] 1. An aromatic dicarboxylic acid as a main acid component, an aliphatic and / or alicyclic dihydroxy compound as a main glycol component, and a phosphorus atom content of a low melting polymer segment having a molecular weight of 400 to 6,000. 50
A two-component composite filament comprising a thermoplastic polyester block copolymer obtained by copolymerizing 0 to 50,000 ppm as a component, having a breaking elongation of 80% or more, a breaking strength of 0.5 g / d or more, and An elastic composite filament having excellent flame retardancy, wherein the elongation recovery after 30% elongation at 80 ° C. is 90% or more. 2. A low melting polymer segment having an aromatic dicarboxylic acid as a main acid component, an aliphatic and / or alicyclic dihydroxy compound as a main glycol component and a phosphorus atom content of 400 to 6000 in molecular weight. 50
A composite filament consisting of a thermoplastic polyester block copolymer obtained by copolymerization of 0 to 50,000 ppm and a thermoplastic polyester block copolymer containing a triazine compound and / or a derivative thereof as one component. An elastic composite filament having excellent flame retardancy, wherein the thermoplastic polyester block copolymer has a limiting oxygen index (LOI) of 20 or more. 3. The flame-retardant elastic according to claim 1, wherein the thermoplastic polyester block copolymer is obtained by copolymerizing a phosphorus compound represented by the following general formula (I). Composite filament. Embedded image (Wherein, R1, is a monovalent ester-forming functional group,
R2 and R3 are the same or different groups, and each is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms,
A is selected from 1, and A represents a divalent or trivalent organic residue. N1 represents 1 or 2, and n2 represents an integer of 0 to 4. ) 4. The flame-retardant polyester block copolymer composition represented by the following general formulas (II) to (IV), wherein the triazine-based compound and / or a derivative thereof comprises: Elastic composite filament with excellent flame retardancy. Embedded image Embedded image Embedded image (Wherein R1, R2, and R3 are a hydrogen atom, an amino group, an alkyl group, an annealed group, and a phenyl group;
3 may be the same or different. ) 5. The composite filament has a substantially sheath-core shape, and the area ratio of the core portion to the fiber cross-sectional area is 5%.
The composite elastic filament excellent in flame retardancy according to claim 1 or 2, wherein the content is 0% or more. 6. The core component has a melting point of 150.degree.
6. The flame-retardant composite elastic filament according to claim 5, wherein the melting point of the sheath component is lower than 20 ° C. and less than 50 ° C. lower than the melting point of the core component. 7. The composite elastic filament having excellent flame retardancy according to claim 5, wherein the thermoplastic polyester block copolymer according to claim 1 is used as a polymer constituting the sheath portion. 8. The flame-retardant material according to claim 7, wherein the thermoplastic polyester block copolymer constituting the sheath portion contains carbon black in an amount of 0.1% by weight or more based on the copolymer. Excellent composite elastic filament.